US4946981A - Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones - Google Patents

Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones Download PDF

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US4946981A
US4946981A US07/211,782 US21178288A US4946981A US 4946981 A US4946981 A US 4946981A US 21178288 A US21178288 A US 21178288A US 4946981 A US4946981 A US 4946981A
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sub
alkyl
hydrogen
oil
sup
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US07/211,782
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Charles G. Carter
David L. Lee
William J. Michaely
Gary W. Kraatz
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Zeneca Inc
Syngenta Crop Protection LLC
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ICI Americas Inc
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Priority claimed from US06/880,370 external-priority patent/US4780127A/en
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Priority to US07/211,782 priority Critical patent/US4946981A/en
Assigned to ICI AMERICAS INC. reassignment ICI AMERICAS INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: STAUFFER CHEMICAL COMPANY DIVISION OF RHONE-POULENC, INC.
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Assigned to ZENECA AG PRODUCTS INC. reassignment ZENECA AG PRODUCTS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ZENECA INC.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
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    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing within the same carbon skeleton a carboxylic group or a thio analogue, or a derivative thereof, and a carbon atom having only two bonds to hetero atoms with at the most one bond to halogen, e.g. keto-carboxylic acids
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/48—Nitro-carboxylic acids; Derivatives thereof
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    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
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    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
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    • A01N41/10—Sulfones; Sulfoxides
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
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    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
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    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/58—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by halogen atoms
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    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
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    • C07C205/61—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms
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    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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    • C07C233/30—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms
    • C07C233/33—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/747—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups containing six-membered aromatic rings
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    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
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    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
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    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • Ser. No. 880,370 is a continuation-in-part application of Ser. No. 772,593, filed Sept. 5, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 634,408, filed July 31, 1984, now abandoned; which in turn is a continuation-in-part application of Ser. No. 587,331, filed Mar. 7, 1984, now abandoned; which in turn is a continuation-inpart of application Ser. No. 532,869, filed Sept. 16, 1983, now abandoned; which in turn is a continuation-in-part application of Ser. No. 464,251, filed Feb. 9, 1983, now abandoned; which in turn is a continuation-in-part application of Ser. No. 361,658, filed Mar. 25, 1982, now abandoned.
  • Ser. No. 880,370 is also a continuation-in-part of application Ser. No. 752,702, filed July 8, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 640,791, filed Aug. 17, 1984, now abandoned, which in turn is a continuation-in-part application of Ser. No. 566,077, filed Dec. 27, 1983, now abandoned; which in turn is a continuation-in-part of application Ser. No. 532,882, filed Sept. 16, 1983, now abandoned.
  • Ser. No. 880,370 is also a continuation-in-part of application Ser. No. 804,026, filed Dec. 3, 1985, now abandoned; which in turn is a continuation of application Ser. No. 683,899, filed Dec. 20, 1984, now abandoned.
  • Ser. No. 880,370 is also a continuation-in-part application of application Ser. No. 802,135, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part of application Ser. No. 683,900, filed Dec. 20, 1984, now abandoned.
  • Ser. No. 880,370 is a also continuation-in-part application of Ser. No. 802,133, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 683,898, filed Dec. 20, 1984, now abandoned.
  • Ser. No. 880,370 is also a continuation-in-part application of application Ser. No. 802,134, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part of application Ser. No. 683,884, filed Dec. 20, 1984, now abandoned.
  • Ser. No. 880,370 is also a continuation-in-part application of Ser. No. 872,067, filed June 9, 1986, now abandoned.
  • the precursor intermediates for these three specifically taught compounds have no or almost no herbicidal activity.
  • Embodiment A of this invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides.
  • the compounds of this embodiment have the following structural formula ##STR4## wherein R and R 1 are hydrogen, C 1 -C 4 alkyl, preferably methyl or isopropyl, R a OC(O)--, where R a is C 1 -C 4 alkyl; most preferably R and R 1 are hydrogen;
  • R 2 is chlorine, bromine, iodine or C 1 -C 4 alkoxy, preferably methoxy; most preferably R 2 is chlorine, bromine or methoxy;
  • R 3 , R 4 and R 5 independently are hydrogen or an aliphatic group, preferably: (1) hydrogen; (2) halogen, preferably chlorine or bromine; (3) C 1 -C 4 alkyl, preferably methyl; (4) C 1 -C 4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl, more preferably trifluoromethyl; (9) R b SO n -- wherein R b is C 1 -C 4 alkyl, preferably methyl, C 1 -C 4 haloalkyl, phenyl, benzyl, --NR d R e wherein R d and R e independently are hydrogen or C 1 -C 4 alkyl; and n is the integer 0, 1 or 2, preferably 2; ##STR5## wherein R c is C 1 -C 4 alkyl and R j is hydrogen or C 1 -C 4 alkyl, preferably methyl
  • R 3 and R 4 can also be (14) C 3 -C 5 alkenyloxy (thio) optionally substituted, preferably with halogen or (15) C 3 -C 5 alkynyloxy (thio), optionally substituted, preferably with halogen.
  • R 3 is chlorine, hydrogen, dimethylamino or methoxy.
  • R 4 is hydrogen, chlorine, nitro, SO 2 CH 3 , SO 2 N(CH 3 ) 2 or trifluoromethoxy.
  • R 5 is hydrogen.
  • Embodiment A' of this invention is an herbicidal composition
  • an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier threfor Preferably, the 2-position of the benzoyl moiety is substituted with chlorine, bromine, iodine or C 1 -C 4 alkoxy; more preferably chlorine, bromine or methoxy; most preferably chlorine.
  • the 5-position of the 1,3-cyclohexanedione moiety can be substituted with one or two C 1 -C 4 alkyl groups, preferably methyl, although such a substitution is not preferred.
  • Embodiment A of this invention can have the following four structural formulae because of tautomerism: ##STR6## wherein R, R 1 , R 2 , R 3 , R 4 and R 5 are as defined above.
  • cations of these bases are inorganic cations such as alkali metals, e.g. lithium, sodium, and potassium, alkaline earth metals, e.g. barium, magnesium, calcium and strontium or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • alkali metals e.g. lithium, sodium, and potassium
  • alkaline earth metals e.g. barium, magnesium, calcium and strontium
  • organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • alkyl and alkoxy include both straight and branched configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
  • Embodiment B of this invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides.
  • the compounds of this embodiment have the following structural formula ##STR8## wherein R 10 is C 1 -C 6 alkyl, preferably C 1 -C 4 , more preferably methyl;
  • R 11 is hydrogen or C 1 -C 6 alkyl, preferably C 1 -C 4 , more preferably methyl or ##STR9## wherein R a is C 1 -C 4 alkyl or R 10 and R 11 together are alkylene having 3 to 6 carbon atoms, most preferably R 11 is hydrogen or methyl;
  • R 12 is chlorine, bromine, iodine, fluorine or C 1 -C 4 alkoxy, preferably methoxy; most preferably R 12 is chlorine, bromine or methoxy;
  • R 13 and R 14 independently are (1) hydrogen or an aliphatic group, preferably hydrogen; (2) halogen, preferably, fluorine, chlorine or bromine; (3) C 1 -C 4 alkyl, preferably methyl; (4) C 1 -C 4 aliphatic alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl, more preferablyy trifluoromethyl; (9) R b SO n -- wherein R b is C 1 -C 4 alkyl, preferably methyl, C 1 -C 4 haloalkyl, phenyl, benzyl, --NR d R e wherein R d and R e independently are hydrogen or C 1 -C 4 alkyl; and n is the integer 0, 1 or 2, preferably 2; ##STR10## wherein R c is C 1 -C 4 alkyl and R j is hydrogen or C 1 -C 4 alkyl
  • R 15 , R 16 , R 17 and R 18 are independently the same or different and are selected from the group consisting of hydrogen, C 1 -C 6 alkyl, preferably C 1 -C 4 alkyl, more preferably methyl, most preferably hydrogen or methyl, and their salts;
  • R 15 and R 16 together may form a substituted or unsubstituted alkylene ring of 2-5 carbon atoms, the preferred substituent being 1 or 2 methyl groups.
  • R 13 is chlorine, hydrogen, methyl, alkylthio or methoxy.
  • R 14 is hydrogen, chlorine, nitro, trifluoromethyl, or R b SO n wherein R b is C 1 -C 4 alkyl, preferably methyl and n is the integer 0, 1 or 2, preferably 2.
  • Embodiment B of the invention can have the following four structural formulae because of tautomerism: ##STR11## wherein R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are as defined above.
  • cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium, alkaline earth metals, e.g. barium, magnesium, calcium and strontium, or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • alkali metals e.g. lithium, sodium, and potassium
  • alkaline earth metals e.g. barium, magnesium, calcium and strontium
  • organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • aliphatic group is used form Embodiments A and B herein in a broad sense to cover a large class of organic groups characterized by being derived from (1) an acylic (open-chain structure) of the paraffin, olefin and acetylene hydrocarbon series and their derivatives or (2) alicyclic compounds.
  • the aliphatic group can have from 1 to 10 carbon atoms.
  • aromatic group is used for Embodiments A and B herein in a broad sense to distinguish from the aliphatic group and includes a group derived from (1) compounds having 6 to 20 carbon atoms and characterized by the presence of at least one benzene ring, including monocyclic, bicyclic and polycyclic hydrocarbons and their derivatives and (2) heterocyclic compounds having 5 to 19 carbon atoms which are similar in structure and are characterized by having an unsaturated ring structure containing at least one atom or other than carbon such as nitrogen, sulfur and oxygen and derivatives of these heterocyclic compounds.
  • alkyl and alkoxy include both straight and branched configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
  • Embodiment C of this invention relates to certain novel 2-(2'-cyanobenzoyl)cyclohexane-1,3-diones as herbicides.
  • the compounds of of this embodiment have the following structural formula ##STR13## wherein R 21 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl, most preferably R 21 is hydrogen or methyl;
  • R 22 is hydrogen; C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl or ##STR14## wherein R a is C 1 -C 4 alkyl, most preferably R 22 is hydrogen or methyl; or R 21 and R 22 together are alkylene having 3 to 6 carbon atoms;
  • R 23 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 23 is hydrogen or methyl;
  • R 24 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 24 is hydrogen or methyl;
  • R 25 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 25 is hydrogen or methyl;
  • R 26 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl, most preferably R 26 is hydrogen;
  • R 27 and R 28 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (39 C 1 -C 4 alkyl, preferably methyl; (4) C 1 -C 4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl, more preferably trifluoromethyl; (9) R b SO n -- wherein n is the integer 0, 1 or 2, preferably 2; and
  • R b is
  • R e C(O)-- wherein R e is C 1 -C 4 alkyl or C 1 -C 4 alkoxy; or
  • R 27 is in the 3-position. Most preferably R 27 is hydrogen and R 28 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R b SO 2 wherein R b is C 1 -C 4 alkyl, preferably methyl.
  • the compounds of this embodiment can have the following four structural formulae because of the tautomerism: ##STR15## wherein R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are as defined above.
  • cations of these bases are inorgaic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • inorgaic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • Embodiment D of this invention relates to 2-(2-nitrobenzoyl)-1,3-cyclohexanediones and their use as herbicides.
  • the compounds have a nitro substitution in the 2-position of the phenyl moiety of their compounds.
  • the nitro substitution imparts exceptional herbicidal activity to the compounds of this invention.
  • Embodiment D' of this invention is an herbicidal composition
  • the 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups.
  • the 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
  • novel compounds of Embodiment D have the following structural formula ##STR17## wherein R 31 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 12 alkyl, more preferably methyl, most preferably R 31 is hydrogen or methyl;
  • R 32 is hydrogen; C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl or ##STR18## wherein R a is C 1 -C 4 alkyl, most preferably R 32 is hydrogen or methyl; or
  • R 31 and R 32 together are alkylene having 3 to 6 carbon atoms
  • R 33 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 33 is hydrogen or methyl;
  • R 34 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 34 is hydrogen or methyl;
  • R 35 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 35 is hydrogen or methyl;
  • R 36 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl, most preferably R 36 is hydrogen;
  • R 37 and R 38 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C 1 -C 4 alkyl, preferably methyl; (4) C 1 -C 4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl, most preferably trifluoromethyl; (9) R b SO n -- wherein n is the integer 0, 1 or 2, preferably 2; and
  • R b is
  • R c and R d independently are hydrogen or C 1 -C 4 alkyl; (11) R e C(O)-- wherein R e is C 1 -C 4 alkyl or C 1 -C 4 alkoxy; or (12) --SO 2 NR c R d wherein R c and R d are as defined, with the proviso that R 37 is not attached to the 6-position.
  • R 37 is in the 3-position. Most preferably R 37 is hydrogen or C 1 -C 4 alkoxy and R 38 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R b SO 2 wherein R b is C 1 -C 4 alkyl, preferably methyl.
  • C 1 -C 4 alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl.
  • halogen includes chlorine, bromine, iodine and fluorine.
  • C 1 -C 4 alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy.
  • haloalkyl includes the eight alkyl groups with one or more hydrogens replaced by chlorine, bromine, iodine or fluorine.
  • the compounds of this invention can have the following four structural formulae because of tautomerism: ##STR19## wherein R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 are as defined above.
  • cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • alkali metals e.g. lithium, sodium, and potassium
  • organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • Embodiment E of this invention relates to 2-(2-benzoyl)-1,3-cyclohexanediones and their use as herbicides.
  • Embodiment E' of this invention is an herbicidal composition
  • the 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are subsituted with one or two methyl groups.
  • the 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
  • n is the integer 0, 1 or 2, preferably 2;
  • R 40 is C 1 -C 4 alkyl, preferably methyl
  • R 41 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl, most preferably R 41 is hydrogen or methyl;
  • R 42 is hydrogen; C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl or ##STR22## wherein R a is C 1 -C 4 , most preferably R 42 is hydrogen or methyl; or
  • R 41 and R 42 together are alkylene having 3 to 6 carbon atoms
  • R 43 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 43 is hydrogen or methyl;
  • R 44 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 44 is hydrogen or methyl;
  • R 45 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 45 is hydrogen or methyl;
  • R 46 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl, most preferably R 46 is hydrogen;
  • R 47 and R 48 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C 1 -C 4 alkyl, preferably methyl; (4) C 1 -C 4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl, more preferably trifluoromethyl; (9) R b SO n -- wherein n is the integer 0, 1 or 2, preferably 2; and
  • R b is
  • R c and R d independently are hydrogen or C 1 -C 4 alkyl; (11) R e C(O)-- wherein R e is C 1 -C 4 alkyl or C 1 -C 4 alkoxy; or (12) --SO 2 NR c R d wherein R c and R d are as defined, with the proviso that R 47 is not attached to the 6-position.
  • R 47 is in the 3-position. Most preferably R 47 is hydrogen or 3-chlorine and R 48 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R b SO 2 wherein R b is C 1 -C 4 alkyl, preferably methyl.
  • C 1 -C 4 alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl.
  • halogen includes chlorine, bromine, iodine and fluorine.
  • C 1 -C 4 alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy.
  • haloalkyl includes the eight alkyl groups with one or more hydrogens replaced by chloro, bromo, iodo or fluoro.
  • the compounds of this invention can have the following four structural formulae because of tautomerism: ##STR23## wherein n, R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 are as defined above.
  • cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium, organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • inorganic cations such as alkali metals e.g. lithium, sodium, and potassium
  • organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • Embodiment F of this invention relates to 2-(2-alkylbenzoyl)-1,3-cyclohexanediones and their use as herbicides.
  • Embodiment F' of this invention is an herbicidal composition
  • an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier therefor wherein the 2-position of the benzoyl moiety is substituted with C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, optionally substituted with halogen, more preferably methyl or trifluoromethyl and the 4-position preferably is substituted with an electron withdrawing group, such as halogen, cyano, trifluoromethyl or nitro.
  • the 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited.
  • the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups.
  • the 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
  • novel compounds of Embodiment F have the following structural formula ##STR25## wherein R 50 is C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, optionally substituted with halogen, more preferably methyl and trifluoromethyl;
  • R 51 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl, most preferably R 51 is hydrogen or methyl;
  • R 52 is hydrogen; C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl or ##STR26## wherein R a is C 1 -C 4 alkyl, most preferably R 52 is hydrogen or methyl; or
  • R 51 and R 52 together are alkylene having 3 to 6 carbon atoms
  • R 53 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 53 is hydrogen or methyl;
  • R 54 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 54 is hydrogen or methyl;
  • R 55 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl; most preferably R 55 is hydrogen or methyl;
  • R 56 is hydrogen or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl, more preferably methyl, most preferably R 56 is hydrogen;
  • R 57 and R 58 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C 1 -C 4 alkyl, preferably methyl; (4) C 1 -C 4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl, more preferably trifluoromethyl; (9) R b SO n -- wherein n is the integer 0, 1 or 2, preferably 2; and
  • R b is
  • R c and R d independently are hydrogen or C 1 -C 4 alkyl; (11) R e C(O)-- wherein R e is C 1 -C 4 alkyl or C 1 -C 4 alkoxy; or (12) --SO 2 NR c R d wherein R c and R d are as defined, with the proviso that R 57 is not attached to the 6-position.
  • C 1 -C 4 alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl.
  • halogen includes chlorine, bromine, iodine and fluorine.
  • C 1 -C 4 alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy.
  • haloalkyl includes the eight alkyl groups with one or more hydrogens replaced by chloro, bromo, iodo or fluoro.
  • R 57 is in the 3-position. Most preferably R 57 is hydrogen and R 58 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R b SO 2 wherein R b is C 1 -C 4 alkyl, preferably methyl.
  • the compounds of this invention can have the following four structural formulae because of tautomerism: ##STR27## wherein R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 and R 58 are as defined above.
  • cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
  • Embodiment G of this invention relates to 2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.
  • Embodiment G' of this invention is an herbicidal composition
  • the 4- and 6-positions of the 1,3,5-cyclohexanetrione moiety are preferably substituted with groups hereinafter defined, most preferably with all methyl groups.
  • the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
  • the novel compounds of Embodiment G have the following structural formula ##STR29## wherein R 60 is hydrogen; halogen; C 1 -C 2 alkyl, preferably methyl; C 1 -C 2 alkoxy, preferably methoxy; nitro; cyano; C 1 -C 2 haloalkyl, preferably trifluoromethyl; R a SO n -- wherein n is 0 or 2, preferably 2 and R a is C 1 -C 2 alkyl, preferably methyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy.
  • R 60 is chlorine, bromine, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, trifluoromethyl, cyano, nitro, C 1 -C 2 alkylthio or C 1 -C 2 alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; and
  • R 61 is hydrogen or C 1 -C 4 alkyl, preferably methyl
  • R 62 is hydrogen or C 1 -C 4 alkyl, preferably methyl
  • R 61 and R 62 together are C 2 -C 5 alkylene
  • R 63 is C 1 -C 4 alkyl, preferably methyl
  • R 64 is C 1 -C 4 alkyl, preferably methyl
  • R 63 and R 64 together are C 2 -C 5 alkylene
  • R 65 and R 66 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C 1 -C 4 alkyl, preferably methyl; (4) C 1 -C 4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl, more preferably trifluoromethyl; (9) R b SO n -- wherein n is the integer 0, 1 or 2, preferably 2; and
  • R b is
  • R 65 is in the 3-position. More preferably R 65 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C 1 -C 4 alkoxy or C 1 -C 4 thioalkyl. Most preferably, R 65 is hydrogen. Preferably R 66 is in the 4-position. Most preferably R 66 is halogen, cyano, trifluoromethyl, or R b SO 2 wherein R b is C 1 -C 4 alkyl, preferably methyl or C 1 -C 4 haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.
  • C 1 -C 4 alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl.
  • halogen includes chlorine, bromine, iodine and fluorine.
  • C 1 -C 4 alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy.
  • C 1 -C 4 haloalkyl includes the alkyl groups defined above under C 1 -C 4 alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.
  • the compounds of this invention can have the following four structural formulae because of tautomerism: ##STR30## wherein R 60 , R 61 , R 62 , R 63 , R 64 , R 65 and R 66 are as defined above.
  • cations of these bases are inorganic cations such as alkalimetals, e.g., lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents are aliphatic or aromatic groups.
  • the salts of this invention can exist in a chelated form.
  • the compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species.
  • the method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.
  • Embodiments A and A' of the present invention can be prepared by the following general method. ##STR32##
  • mole amounts of the dione and substituted benzoyl cyanide are used, along with a slight mole excess of zinc chloride.
  • the two reactants and the zinc chloride are combined in a solvent such as methylene chloride.
  • a slight mole excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for 5 hours.
  • the reaction product is worked up by conventional techniques.
  • 1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na 2 CO 3 four times.
  • the aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product.
  • the crude product was dissolved in ether and stirred with 250 ml of 5% copper (II) acetate.
  • the resulting copper salt was filtered, washed with ether and stirred with 6N hydrochloric acid to destroy the salt.
  • the extract was washed with ether to yield 22.15 grams of the desired product m.p. 138°-140° C. (77.7% yield). The structure was confirmed by instrumental analysis.
  • Embodiment B of the present invention can be prepared by the following general method. ##STR34##
  • mole amounts of the dione and substituted benzoyl cyanide are used, along with a slight mole excess of zinc chloride.
  • the two reactants and the zinc chloride are combined in a solvent such as methylene chloride.
  • a slight mole excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for 5 hours.
  • the reaction product is worked up by conventional techniques.
  • Embodiment C of the present invention can be prepared by the following general method. ##STR36##
  • step (1) mole amounts of the dione and substituted benzoyl chloride are used, along with a slight mole excess of triethylamine.
  • the two reactants are combined in a solvent such as methylene chloride.
  • the triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for several hours.
  • step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the triethylamine, preferably 2 moles of the triethylamine and up to 0.5 mole, preferably 0.1 mole of a cyanide source (e.g., potassium cyanide or acetone cyanohydrin).
  • a cyanide source e.g., potassium cyanide or acetone cyanohydrin.
  • the substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
  • reaction (a) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR40## wherein R 27 and R 28 are as previously defined.
  • reaction (b) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
  • Triethylamine (4.4 ml, 32 mmol) and acetone cyanohydrin (5 drops) were added and the solution stirred for two hours. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K 2 CO 3 . The aqueous extract was acidified with concentrated hydrochloric acid and extracted with ether. The ether was washed with water and brine, dried (MgSO 4 ) and concentrated under vacuum. The residue was purified by silica gel chromatography, yielding 1.2 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
  • Embodiments D and D' of the present invention can be prepared by the following two-step general method.
  • the process proceeds via the production of an enol ester intermediate as shown in reaction (1).
  • the final product is obtained by rearrangement of the enol ester as shown in reaction (2).
  • the two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1).
  • R 31 through R 38 and moderate base are as defined and X is halogen, preferably chlorine, C 1 -C 4 alkyl-C(O)--O--, C 1 -C 4 alkoxy-C(O)--O-- or ##STR43## wherein R 37 and R 38 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C 1 -C 6 alkylamine, alkali metal carbonate or alkali metal phosphate.
  • step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base.
  • the two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide.
  • the base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete.
  • step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin).
  • the cyanide source e.g., potassium cyanide or acetone cyanohydrin.
  • the mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.
  • cyanide source refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
  • the process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
  • Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C 2 -C 5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
  • the cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
  • Moderate base is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively).
  • Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
  • the base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
  • phase transfer catalyst When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
  • a number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product.
  • a preferred solvent for this reaction is 1,2-dichloroethane.
  • Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
  • the rearrangementt may be conducted at temperatures up to about 50° C.
  • the substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
  • reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR47## wherein R 37 and R 38 are as previously defined.
  • reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR48## wherein R 37 and R 38 are as previously defined.
  • reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
  • Triethylamine (3.4 ml, 25 mmol) was added dropwise to a methylene chloride solution of 2-nitrobenzoyl chloride (3.5 g, 19 mmol) and 5,5-dimethylcyclohexanedione (2.4 g, 19 mmol). After stirring for one hour at room temperature an additional 3 equivalents of triethylamine and 0.4 ml acetone cyanohydrin were added. The solution was stirred for 2.5 hours, then washed with 2N HCl and extracted with 5% potassium carbonate solution. The basic extracts were acidified with 2N HCl and extracted with ether. The ether portion was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under vacuum.
  • Embodiments E and E' of the present invention can be prepared by the following two or three step general method.
  • the process proceeds via the production of an enol ester intermediate as shown in reaction (1).
  • the final product is obtained by rearrangement of the enol ester as shown in reaction (2).
  • the two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1).
  • moderate base and R 40 through R 48 are defined herein, and X is halogen, preferably chlorine, C 1 -C 4 alkyl-C(O)--O--, C 1 -C 4 alkoxy-C(O)--O-- or ##STR52## wherein R 40 , R 47 and R 48 in this portion of the moledule are identical with those in the reactant shown above, and the moderate base is as defined, preferably tri-C 1 -C 6 alkylamine, alkali metal carbonate or alkali metal phosphate.
  • step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base.
  • the two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide.
  • the base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete.
  • step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin).
  • the cyanide source e.g., potassium cyanide or acetonecyanohydrin.
  • the mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.
  • cyanide source refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
  • the process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
  • Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C 2 -C 5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
  • the cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
  • Moderate base is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively).
  • Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
  • the base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
  • phase transfer catalyst When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
  • a number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product.
  • a preferred solvent for this reaction is 1,2-dichloroethane.
  • Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
  • the rearrangement may be conducted at temperatures up to about 50° C. ##STR54## wherein n is 1 or 2.
  • step (3) a mole of the reaction product of step (2) is reacted with a slight mole or two mole excess of of an oxidizing agent such as m-chloroperbenzoic acid after being dissolved in a solvent such as methylene chloride. After completion of the reaction, the resulting mixture is stripped under vacuum. The residue is purified by silica gel chromatography to yield the desired product.
  • an oxidizing agent such as m-chloroperbenzoic acid
  • the substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
  • reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR57## wherein R 40 , R 47 and R 48 are as previously defined.
  • reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques.
  • R 40 , R 47 and R 48 are as defined and X is chlorine, bromine or iodine.
  • reaction (c) the substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.
  • Triethylamine (2.5 equivalents) and acetone cyanohydrin (0.4 ml) were added and the solution stirred for 45 minutes at room temperature. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K 2 CO 3 . The aqueous extract was acidified with hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO 4 ) and concentrated under vacuum. The residue was purified by trituration with ether, yielding 5.0 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy (nmr), infrared spectroscopy (ir) and mass spectroscopy (ms).
  • nmr nuclear magnetic resonance spectroscopy
  • ir infrared spectroscopy
  • ms mass spectroscopy
  • Embodiments F and F' of the present invention can be prepared by the following two-step general method.
  • the process proceeds via the production of an enol ester intermediate as shown in reaction (1).
  • the final product is obtained by rearrangement of the enol ester as shown in reaction (2).
  • the two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1).
  • R 50 through R 58 are as defined and X is halogen, preferably chlorine, C 1 -C 4 alkyl-C(O)--O--, C 1 -C 4 alkoxy-C(O)--O-- or ##STR63## wherei R 50 , R 57 and R 58 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C 1 -C 6 alkylamine, alkali metal carbonate or alkali metal phosphate.
  • step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base.
  • the two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide.
  • the base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete.
  • reaction product is worked up by conventional techniques. ##STR64## wherein R 50 through R 58 are as defined.
  • step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin).
  • the cyanide source e.g., potassium cyanide or acetone cyanohydrin.
  • the mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 80° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.
  • cyanide source refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
  • the process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
  • Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C 2 -C 5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
  • the cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
  • Moderate base is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively).
  • Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
  • the base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
  • phase transfer catalyst When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
  • a number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product.
  • a preferred solvent for this reaction is 1,2-dichloroethane.
  • Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
  • the rearrangement may be conducted at temperatures up to about 50° C.
  • the substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
  • reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR67## wherein R 50 , R 57 and R 58 are as previously defined.
  • reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques.
  • R 50 , R 57 and R 58 are as defined and X is chlorine, bromine or iodine.
  • the substituted aromatic halide is allowed to react with magnesium in a solvent such as ether.
  • the solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.
  • the aqueous extract was acidified with concentrated hydrochloric acid and extracted with ether.
  • the ether was washed with brine, dried (MgSO 4 ) and concentrated under vacuum.
  • the resulting oil was purified on a silica gel column (80:20:1 hexane:ethyl acetate: acetic acid-eluent), yielding 1.5 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
  • Embodiment G and G' of the present invention can be prepared by the following two-step general method.
  • the process proceeds via the production of an enol ester intermediate as shown in reaction (1).
  • the final product is obtained by rearrangement of the enol ester as shown in reaction (2).
  • the two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1).
  • R 60 through R 66 and moderate base are as defined and X is halogen, preferably chlorine, C 1 -C 4 alkyl-C(O)--O--, C 1 -C 4 alkoxy-C(O)--O-- or ##STR71## wherein R 60 , R 65 and R 66 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C 1 -C 6 alkylamine alkali metal carbonate or alkali metal phosphate.
  • step (1) mole amounts of the trione and substituted benzoyl reactant are used, along with a mole amount or excess of the base.
  • the two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide.
  • the base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete.
  • step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin).
  • the cyanide source e.g., potassium cyanide or acetone cyanohydrin.
  • the mixture is stirred in a reaction pot until the rearrangment is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.
  • cyanide source refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
  • the process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
  • Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C 2 -C 5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
  • the cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
  • Moderate base is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively).
  • Moderate bases suitable for use in this embodiment include both organic bases, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
  • the base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
  • phase transfer catalyst When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction.
  • Particularly suitable phase transfer catalysts are the crown ethers.
  • a number of different solvents are useful in this process, depending on the nature of the acid halide or the acylated porduct.
  • a preferred solvent for this reaction is 1,2-dichloroethane.
  • Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
  • the rearrangement may be conducted at temperatures up to about 50° C.
  • the substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
  • reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR75## wherein R 60 , R 65 and R 66 are as previously defined.
  • reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR76## wherein R 60 , R 65 and R 66 are as previously defined.
  • reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
  • Triethylamine (5 ml, 3.5 equivalents) and acetone cyanohydrin (0.5 g, 0.6 equivalent) were added and the mixture stirred at room temperature for 4 hours. After dilution with ether, the solution was washed with 1N HCl and extracted with 5% K 2 CO 3 . The basic extract was acidified with HCl and extracted with ether. The ether extract was washed with brine, dried over MgSO 4 and concentrated under vacuum, yielding 2.2 g of crude product. This was recrystallized from benzene to remove syncarpic acid still present. Concentration of the mother liquor under vacuum gave 1.7 g of the desired product as an oil, which solidifed on standing (m.p. 76°-82° C.). It was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
  • the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species.
  • Selected compounds of this invention were tested as herbicides in the following manner.
  • FT green foxtail
  • WG Watergrass
  • WO wild oat
  • AMG African pigweed
  • VL velvetleaf
  • MD Indian mustard
  • PW redroot pigweed
  • CD Redroot crispus
  • YNG yellow nutsedge
  • the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling.
  • the injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.
  • This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the eight different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.
  • the process was generally similar to the pre-emergence herbicide test described above except that only 300 or 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.
  • Redroot pigweed (PW) and curly doct (CD) were eliminated in this test and the following weed species were added:
  • the process was generally similar to the post-emergence herbicide test described above except that only 300 or 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.
  • the compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations.
  • the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application.
  • these active herbicidal compounds or salts can be formulated as graules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient.
  • a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants.
  • the wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid.
  • Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents.
  • Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.
  • Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents.
  • these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated.
  • the percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.
  • Granular formulations wherein the toxicant is carried on relatively coarse particles are usually applied without dilution to the area in which suppression of vegetation is desired.
  • Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant.
  • Granular formulations normally are prepared to contain about 0.1% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
  • Typical wetting, dispersing or emulsifing agents and adjuvants used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines; and other types of surface-active agents, many of which are available in commerce.
  • the surface-active agent when used, normally comprises from 0.1% to 30% by weight of the herbicidal composition.
  • Dusts which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.
  • Pastes which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredients by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.
  • compositions for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xylene and other organic solvents.
  • a dispersant in which it is completely soluble at the desired concentration
  • Pressurized sprays typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.
  • the phytotoxic compositions of this invention can be applied to the plants in the conventional manner.
  • the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters.
  • the compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages.
  • the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface.
  • the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil.
  • the phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.
  • the herbicidal compound can be substituted with the herbicidal salt of the compound.
  • salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.
  • the phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants.
  • Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate.

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Abstract

Compounds of the formula <IMAGE> wherein R is halogen, C1-C4 alkoxy, C1-C4 alkyl, C1-C4 haloalkyl, cyano, nitro, S(O)nR wherein R is C1-C4 alkyl and n is the integer 0, 1 or 2; and R2 through R8 are hydrogen or certain substituents, their salts, herbicidal compositions containing the compound or salts and the herbicidal use thereof.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
This is a divisional of application Ser. No. 880,370, filed June 30, 1986, now U.S. Pat. No. 4,780,127.
Ser. No. 880,370 is a continuation-in-part application of Ser. No. 772,593, filed Sept. 5, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 634,408, filed July 31, 1984, now abandoned; which in turn is a continuation-in-part application of Ser. No. 587,331, filed Mar. 7, 1984, now abandoned; which in turn is a continuation-inpart of application Ser. No. 532,869, filed Sept. 16, 1983, now abandoned; which in turn is a continuation-in-part application of Ser. No. 464,251, filed Feb. 9, 1983, now abandoned; which in turn is a continuation-in-part application of Ser. No. 361,658, filed Mar. 25, 1982, now abandoned.
Ser. No. 880,370 is also a continuation-in-part of application Ser. No. 752,702, filed July 8, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 640,791, filed Aug. 17, 1984, now abandoned, which in turn is a continuation-in-part application of Ser. No. 566,077, filed Dec. 27, 1983, now abandoned; which in turn is a continuation-in-part of application Ser. No. 532,882, filed Sept. 16, 1983, now abandoned.
Ser. No. 880,370 is also a continuation-in-part of application Ser. No. 804,026, filed Dec. 3, 1985, now abandoned; which in turn is a continuation of application Ser. No. 683,899, filed Dec. 20, 1984, now abandoned.
Ser. No. 880,370 is also a continuation-in-part application of application Ser. No. 802,135, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part of application Ser. No. 683,900, filed Dec. 20, 1984, now abandoned.
Ser. No. 880,370 is a also continuation-in-part application of Ser. No. 802,133, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 683,898, filed Dec. 20, 1984, now abandoned.
Ser. No. 880,370 is also a continuation-in-part application of application Ser. No. 802,134, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part of application Ser. No. 683,884, filed Dec. 20, 1984, now abandoned.
Ser. No. 880,370 is also a continuation-in-part application of Ser. No. 872,067, filed June 9, 1986, now abandoned.
Applicants specifically incorporate by reference the contents of the above listed U.S. patent applications.
BACKGROUND OF THE INVENTION
Compounds having the structural formula ##STR2## wherein X can be alkyl, n can be 0, 1, or 2, and R1 can be phenyl or substituted phenyl are described in Japanese Patent Application No. 84632-1974 as being intermediates for the preparation of herbicidal compounds of the formula ##STR3## wherein R1, X, and n are as defined above and R2 is alkyl, alkenyl, or alkynyl. Specifically taught herbicidal compounds of this latter group are those where n is 2, X is 5,5-dimethyl, R2 is allyl and R1 is phenyl, 4-chlorophenyl or 4-methoxyphenyl.
The precursor intermediates for these three specifically taught compounds have no or almost no herbicidal activity.
DESCRIPTION OF THE INVENTION
Embodiment A of this invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of this embodiment have the following structural formula ##STR4## wherein R and R1 are hydrogen, C1 -C4 alkyl, preferably methyl or isopropyl, Ra OC(O)--, where Ra is C1 -C4 alkyl; most preferably R and R1 are hydrogen;
R2 is chlorine, bromine, iodine or C1 -C4 alkoxy, preferably methoxy; most preferably R2 is chlorine, bromine or methoxy;
R3, R4 and R5 independently are hydrogen or an aliphatic group, preferably: (1) hydrogen; (2) halogen, preferably chlorine or bromine; (3) C1 -C4 alkyl, preferably methyl; (4) C1 -C4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C1 -C4 haloalkyl, more preferably trifluoromethyl; (9) Rb SOn -- wherein Rb is C1 -C4 alkyl, preferably methyl, C1 -C4 haloalkyl, phenyl, benzyl, --NRd Re wherein Rd and Re independently are hydrogen or C1 -C4 alkyl; and n is the integer 0, 1 or 2, preferably 2; ##STR5## wherein Rc is C1 -C4 alkyl and Rj is hydrogen or C1 -C4 alkyl, preferably methyl; (11) Rf C(O) wherein Rf is hydrogen, C1 -C4 alkyl, C1 -C4 haloalkyl, C1 -C4 alkoxy; (12) --NRg Rh wherein Rg and Rh independently are hydrogen or C1 -C4 alkyl; or less preferably (13) R3 and R4 together can form a ring structure with two adjacent carbon atoms of the phenyl ring.
R3 and R4 can also be (14) C3 -C5 alkenyloxy (thio) optionally substituted, preferably with halogen or (15) C3 -C5 alkynyloxy (thio), optionally substituted, preferably with halogen.
Most preferably, R3 is chlorine, hydrogen, dimethylamino or methoxy. Preferably, R4 is hydrogen, chlorine, nitro, SO2 CH3, SO2 N(CH3)2 or trifluoromethoxy. Preferably, R5 is hydrogen.
Embodiment A' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier threfor. Preferably, the 2-position of the benzoyl moiety is substituted with chlorine, bromine, iodine or C1 -C4 alkoxy; more preferably chlorine, bromine or methoxy; most preferably chlorine. The 5-position of the 1,3-cyclohexanedione moiety can be substituted with one or two C1 -C4 alkyl groups, preferably methyl, although such a substitution is not preferred.
The compounds of Embodiment A of this invention can have the following four structural formulae because of tautomerism: ##STR6## wherein R, R1, R2, R3, R4 and R5 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR7## wherein R, R1, R2, R3, R4 and R5 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals, e.g. lithium, sodium, and potassium, alkaline earth metals, e.g. barium, magnesium, calcium and strontium or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
In the above description of the compounds of this invention, alkyl and alkoxy include both straight and branched configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
Embodiment B of this invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of this embodiment have the following structural formula ##STR8## wherein R10 is C1 -C6 alkyl, preferably C1 -C4, more preferably methyl;
R11 is hydrogen or C1 -C6 alkyl, preferably C1 -C4, more preferably methyl or ##STR9## wherein Ra is C1 -C4 alkyl or R10 and R11 together are alkylene having 3 to 6 carbon atoms, most preferably R11 is hydrogen or methyl;
R12 is chlorine, bromine, iodine, fluorine or C1 -C4 alkoxy, preferably methoxy; most preferably R12 is chlorine, bromine or methoxy;
R13 and R14 independently are (1) hydrogen or an aliphatic group, preferably hydrogen; (2) halogen, preferably, fluorine, chlorine or bromine; (3) C1 -C4 alkyl, preferably methyl; (4) C1 -C4 aliphatic alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C1 -C4 haloalkyl, more preferablyy trifluoromethyl; (9) Rb SOn -- wherein Rb is C1 -C4 alkyl, preferably methyl, C1 -C4 haloalkyl, phenyl, benzyl, --NRd Re wherein Rd and Re independently are hydrogen or C1 -C4 alkyl; and n is the integer 0, 1 or 2, preferably 2; ##STR10## wherein Rc is C1 -C4 alkyl and Rj is hydrogen or C1 -C4 alkyl, preferably methyl; (11) Rf C(O) wherein Rf is hydrogen, C1 -C4 alkyl, C1 -C4 haloalkyl, C1 -C4 alkoxy; (12) --NRg Rh wherein Rg and Rh independently are hydrogen or C1 -C4 alkyl; (13) C1 -C4 alkylthio or less preferably (14) R13 and R14 together can form a ring structure with two adjacent carbon atoms of the phenyl ring to which they are attached or less preferably (15) R13 and R14 are the groups phenoxy or substituted phenoxy wherein the substituent is halogen or halomethyl or both;
R15, R16, R17 and R18 are independently the same or different and are selected from the group consisting of hydrogen, C1 -C6 alkyl, preferably C1 -C4 alkyl, more preferably methyl, most preferably hydrogen or methyl, and their salts;
provided, however, that R15 and R16 together may form a substituted or unsubstituted alkylene ring of 2-5 carbon atoms, the preferred substituent being 1 or 2 methyl groups.
More preferably, R13 is chlorine, hydrogen, methyl, alkylthio or methoxy. Preferably R14 is hydrogen, chlorine, nitro, trifluoromethyl, or Rb SOn wherein Rb is C1 -C4 alkyl, preferably methyl and n is the integer 0, 1 or 2, preferably 2.
The compounds of Embodiment B of the invention can have the following four structural formulae because of tautomerism: ##STR11## wherein R10, R11, R12, R13, R14, R15, R16, R17 and R18 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR12## wherein R10, R11, R12, R13, R14, R15, R16, R17 and R18 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium, alkaline earth metals, e.g. barium, magnesium, calcium and strontium, or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
The term "aliphatic group" is used form Embodiments A and B herein in a broad sense to cover a large class of organic groups characterized by being derived from (1) an acylic (open-chain structure) of the paraffin, olefin and acetylene hydrocarbon series and their derivatives or (2) alicyclic compounds. The aliphatic group can have from 1 to 10 carbon atoms.
The term "aromatic group" is used for Embodiments A and B herein in a broad sense to distinguish from the aliphatic group and includes a group derived from (1) compounds having 6 to 20 carbon atoms and characterized by the presence of at least one benzene ring, including monocyclic, bicyclic and polycyclic hydrocarbons and their derivatives and (2) heterocyclic compounds having 5 to 19 carbon atoms which are similar in structure and are characterized by having an unsaturated ring structure containing at least one atom or other than carbon such as nitrogen, sulfur and oxygen and derivatives of these heterocyclic compounds.
In the above description of the compounds of this invention alkyl and alkoxy include both straight and branched configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
Embodiment C of this invention relates to certain novel 2-(2'-cyanobenzoyl)cyclohexane-1,3-diones as herbicides. The compounds of of this embodiment have the following structural formula ##STR13## wherein R21 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl, most preferably R21 is hydrogen or methyl;
R22 is hydrogen; C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl or ##STR14## wherein Ra is C1 -C4 alkyl, most preferably R22 is hydrogen or methyl; or R21 and R22 together are alkylene having 3 to 6 carbon atoms;
R23 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R23 is hydrogen or methyl;
R24 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R24 is hydrogen or methyl;
R25 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R25 is hydrogen or methyl;
R26 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl, most preferably R26 is hydrogen;
R27 and R28 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (39 C1 -C4 alkyl, preferably methyl; (4) C1 -C4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C1 -C4 haloalkyl, more preferably trifluoromethyl; (9) Rb SOn -- wherein n is the integer 0, 1 or 2, preferably 2; and
Rb is
(a) C1 -C4 alkyl, preferably methyl;
(b) C1 -C4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NRc Rd wherein Rc and Rd independently are hydrogen or C1 -C4 alkyl;
(11) Re C(O)-- wherein Re is C1 -C4 alkyl or C1 -C4 alkoxy; or
(12) --SO2 NRc Rd wherein Rc and Rd are as defined, with the proviso that R27 is not attached to the 6-position.
Preferably, R27 is in the 3-position. Most preferably R27 is hydrogen and R28 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or Rb SO2 wherein Rb is C1 -C4 alkyl, preferably methyl.
Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.
The compounds of this embodiment can have the following four structural formulae because of the tautomerism: ##STR15## wherein R21, R22, R23, R24, R25, R26, R27 and R28 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR16## wherein R21, R22, R23, R24, R25, R26, R27 and R28 are as defined above.
Examples of cations of these bases are inorgaic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
Embodiment D of this invention relates to 2-(2-nitrobenzoyl)-1,3-cyclohexanediones and their use as herbicides.
The compounds have a nitro substitution in the 2-position of the phenyl moiety of their compounds. The nitro substitution imparts exceptional herbicidal activity to the compounds of this invention.
Embodiment D' of this invention is an herbicidal composition comprising an herbicidally active 2-(2-nitrobenzoyl)-1,3-cyclohexanedione and an inert carrier therefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment D have the following structural formula ##STR17## wherein R31 is hydrogen or C1 -C4 alkyl, preferably C1 -C12 alkyl, more preferably methyl, most preferably R31 is hydrogen or methyl;
R32 is hydrogen; C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl or ##STR18## wherein Ra is C1 -C4 alkyl, most preferably R32 is hydrogen or methyl; or
R31 and R32 together are alkylene having 3 to 6 carbon atoms;
R33 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R33 is hydrogen or methyl;
R34 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R34 is hydrogen or methyl;
R35 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R35 is hydrogen or methyl;
R36 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl, most preferably R36 is hydrogen;
R37 and R38 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C1 -C4 alkyl, preferably methyl; (4) C1 -C4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C1 -C4 haloalkyl, most preferably trifluoromethyl; (9) Rb SOn -- wherein n is the integer 0, 1 or 2, preferably 2; and
Rb is
(a) C1 -C4 alkyl, preferably methyl;
(b) C1 -C4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NRc Rd wherein Rc and Rd independently are hydrogen or C1 -C4 alkyl; (11) Re C(O)-- wherein Re is C1 -C4 alkyl or C1 -C4 alkoxy; or (12) --SO2 NRc Rd wherein Rc and Rd are as defined, with the proviso that R37 is not attached to the 6-position.
Preferably, R37 is in the 3-position. Most preferably R37 is hydrogen or C1 -C4 alkoxy and R38 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or Rb SO2 wherein Rb is C1 -C4 alkyl, preferably methyl.
The term "C1 -C4 alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C1 -C4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chlorine, bromine, iodine or fluorine.
Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.
The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR19## wherein R31, R32, R33, R34, R35, R36, R37 and R38 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR20## wherein R31, R32, R33, R34, R35, R36, R37 and R38 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
Embodiment E of this invention relates to 2-(2-benzoyl)-1,3-cyclohexanediones and their use as herbicides.
Embodiment E' of this invention is an herbicidal composition comprising an herbicidally active 2-(2-C1 -C4 alkylthio, C1 -C4 alkylsulfinyl or C1 -C4 alkylsulfonyl benzoyl)-1,3-cyclohexanedione and an inert carrier therefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are subsituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment E have the structural formula ##STR21## wherein n is the integer 0, 1 or 2, preferably 2;
R40 is C1 -C4 alkyl, preferably methyl;
R41 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl, most preferably R41 is hydrogen or methyl;
R42 is hydrogen; C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl or ##STR22## wherein Ra is C1 -C4, most preferably R42 is hydrogen or methyl; or
R41 and R42 together are alkylene having 3 to 6 carbon atoms;
R43 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R43 is hydrogen or methyl;
R44 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R44 is hydrogen or methyl;
R45 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R45 is hydrogen or methyl;
R46 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl, most preferably R46 is hydrogen;
R47 and R48 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C1 -C4 alkyl, preferably methyl; (4) C1 -C4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C1 -C4 haloalkyl, more preferably trifluoromethyl; (9) Rb SOn -- wherein n is the integer 0, 1 or 2, preferably 2; and
Rb is
(a) C1 -C4 alkyl, preferably methyl;
(b) C1 -C4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NRc Rd wherein Rc and Rd independently are hydrogen or C1 -C4 alkyl; (11) Re C(O)-- wherein Re is C1 -C4 alkyl or C1 -C4 alkoxy; or (12) --SO2 NRc Rd wherein Rc and Rd are as defined, with the proviso that R47 is not attached to the 6-position.
Preferably, R47 is in the 3-position. Most preferably R47 is hydrogen or 3-chlorine and R48 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or Rb SO2 wherein Rb is C1 -C4 alkyl, preferably methyl.
The term "C1 -C4 " alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C1 -C4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chloro, bromo, iodo or fluoro.
Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.
The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR23## wherein n, R40, R41, R42, R43, R44, R45, R46, R47 and R48 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR24## wherein n, R40, R41, R42, R43, R44, R45, R46, R47 and R48 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium, organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
Embodiment F of this invention relates to 2-(2-alkylbenzoyl)-1,3-cyclohexanediones and their use as herbicides.
Embodiment F' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier therefor wherein the 2-position of the benzoyl moiety is substituted with C1 -C4 alkyl, preferably C1 -C2 alkyl, optionally substituted with halogen, more preferably methyl or trifluoromethyl and the 4-position preferably is substituted with an electron withdrawing group, such as halogen, cyano, trifluoromethyl or nitro. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment F have the following structural formula ##STR25## wherein R50 is C1 -C4 alkyl, preferably C1 -C2 alkyl, optionally substituted with halogen, more preferably methyl and trifluoromethyl;
R51 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl, most preferably R51 is hydrogen or methyl;
R52 is hydrogen; C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl or ##STR26## wherein Ra is C1 -C4 alkyl, most preferably R52 is hydrogen or methyl; or
R51 and R52 together are alkylene having 3 to 6 carbon atoms;
R53 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R53 is hydrogen or methyl;
R54 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R54 is hydrogen or methyl;
R55 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl; most preferably R55 is hydrogen or methyl;
R56 is hydrogen or C1 -C4 alkyl, preferably C1 -C2 alkyl, more preferably methyl, most preferably R56 is hydrogen;
R57 and R58 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C1 -C4 alkyl, preferably methyl; (4) C1 -C4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C1 -C4 haloalkyl, more preferably trifluoromethyl; (9) Rb SOn -- wherein n is the integer 0, 1 or 2, preferably 2; and
Rb is
(a) C1 -C4 alkyl, preferably methyl;
(b) C1 -C4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NRc Rd wherein Rc and Rd independently are hydrogen or C1 -C4 alkyl; (11) Re C(O)-- wherein Re is C1 -C4 alkyl or C1 -C4 alkoxy; or (12) --SO2 NRc Rd wherein Rc and Rd are as defined, with the proviso that R57 is not attached to the 6-position.
The term "C1 -C4 alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C1 -C4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chloro, bromo, iodo or fluoro.
Preferably, R57 is in the 3-position. Most preferably R57 is hydrogen and R58 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or Rb SO2 wherein Rb is C1 -C4 alkyl, preferably methyl.
Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.
The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR27## wherein R50, R51, R52, R53, R54, R55, R56, R57 and R58 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR28## wherein R50, R51, R52, R53, R54, R55, R56, R57 and R58 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
Embodiment G of this invention relates to 2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.
Embodiment G' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione and an inert carrier therefor. The 4- and 6-positions of the 1,3,5-cyclohexanetrione moiety are preferably substituted with groups hereinafter defined, most preferably with all methyl groups. The benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment G have the following structural formula ##STR29## wherein R60 is hydrogen; halogen; C1 -C2 alkyl, preferably methyl; C1 -C2 alkoxy, preferably methoxy; nitro; cyano; C1 -C2 haloalkyl, preferably trifluoromethyl; Ra SOn -- wherein n is 0 or 2, preferably 2 and Ra is C1 -C2 alkyl, preferably methyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy. Preferably, R60 is chlorine, bromine, C1 -C2 alkyl, C1 -C2 alkoxy, trifluoromethyl, cyano, nitro, C1 -C2 alkylthio or C1 -C2 alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; and
R61 is hydrogen or C1 -C4 alkyl, preferably methyl;
R62 is hydrogen or C1 -C4 alkyl, preferably methyl; or
R61 and R62 together are C2 -C5 alkylene;
R63 is C1 -C4 alkyl, preferably methyl;
R64 is C1 -C4 alkyl, preferably methyl; or
R63 and R64 together are C2 -C5 alkylene;
R65 and R66 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C1 -C4 alkyl, preferably methyl; (4) C1 -C4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C1 -C4 haloalkyl, more preferably trifluoromethyl; (9) Rb SOn -- wherein n is the integer 0, 1 or 2, preferably 2; and
Rb is
(a) C1 -C4 alkyl, preferably methyl;
(b) C1 -C4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NRc Rd wherein Rc and Rd independently are hydrogen or C1 -C4 alkyl; (11) Re C(O)-- wherein Re is C1 -C4 alkyl or C1 -C4 alkoxy; (12) --SO2 NRc Rd wherein Rc and Rd are as defined; or (13) --N(Rc)C(O)Rd wherein Rc and Rd are as defined.
Preferably R65 is in the 3-position. More preferably R65 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C1 -C4 alkoxy or C1 -C4 thioalkyl. Most preferably, R65 is hydrogen. Preferably R66 is in the 4-position. Most preferably R66 is halogen, cyano, trifluoromethyl, or Rb SO2 wherein Rb is C1 -C4 alkyl, preferably methyl or C1 -C4 haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.
The term "C1 -C4 alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C1 -C4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C1 -C4 haloalkyl" includes the alkyl groups defined above under C1 -C4 alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.
Salts of the above-described compounds (as defined hereinafter) are included within the scope of the instant invention.
The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR30## wherein R60, R61, R62, R63, R64, R65 and R66 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following four resonance forms: ##STR31## wherein R60, R61, R62, R63, R64, R65 and R66 are as defined above.
Examples of cations of these bases are inorganic cations such as alkalimetals, e.g., lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents are aliphatic or aromatic groups.
Those skilled in the art will recognize in considering the salts of this invention that varying degrees os association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.
The compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.
The compounds of Embodiments A and A' of the present invention can be prepared by the following general method. ##STR32##
Generally, mole amounts of the dione and substituted benzoyl cyanide are used, along with a slight mole excess of zinc chloride. The two reactants and the zinc chloride are combined in a solvent such as methylene chloride. A slight mole excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for 5 hours.
The reaction product is worked up by conventional techniques.
The above-described substituted benzoyl cyanide can be prepared according to the teaching of T. S. Oakwood and C. A. Weisgerber, Organic Synthesis Collected, Vol. III, pp. 122 (1955).
The following example teaches the synthesis of a representative compound of Embodiments A and A' of this invention.
EXAMPLE 1-A,A' 2-(2,4-Dichlorobenzoyl)-cyclohexane-1,3-dione ##STR33##
1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na2 CO3 four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was dissolved in ether and stirred with 250 ml of 5% copper (II) acetate. The resulting copper salt was filtered, washed with ether and stirred with 6N hydrochloric acid to destroy the salt. The extract was washed with ether to yield 22.15 grams of the desired product m.p. 138°-140° C. (77.7% yield). The structure was confirmed by instrumental analysis.
The compounds of Embodiment B of the present invention can be prepared by the following general method. ##STR34##
Generally, mole amounts of the dione and substituted benzoyl cyanide are used, along with a slight mole excess of zinc chloride. The two reactants and the zinc chloride are combined in a solvent such as methylene chloride. A slight mole excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for 5 hours.
The reaction product is worked up by conventional techniques.
The above-described substituted benzoyl cyanide can be prepared according to the teaching of T. S. Oakwood and C. A. Weisgerber, Organic Synthesis Collected, Vol. III, pp. 122 (1955).
The following example teaches the synthesis of a representative compound of Embodiment B of this invention.
EXAMPLE 1-B 4,4-Dimethyl-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione ##STR35##
4,4-Dimethyl-1,3-cyclohexanedione [14.0 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na2 CO3 four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was chromatographed (2% AcOH/CH2 Cl2) in 5 g aliquots then reduced on rotavap under reduced pressure at 50° C. for 30 minutes to remove AcOH. This yielded an oil (40% yield). The structure was confirmed by instrumental analysis.
The compounds of Embodiment C of the present invention can be prepared by the following general method. ##STR36##
Generally, in step (1) mole amounts of the dione and substituted benzoyl chloride are used, along with a slight mole excess of triethylamine. The two reactants are combined in a solvent such as methylene chloride. The triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for several hours.
The reaction product is worked up by conventional techniques. ##STR37##
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the triethylamine, preferably 2 moles of the triethylamine and up to 0.5 mole, preferably 0.1 mole of a cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot for about one hour at room temperature and the desired product is recovered by conventional techniques.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR38## wherein R27 and R28 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are two representative examples of the methods described therein. ##STR39## wherein R27 and R28 are as previously defined.
In reaction (a) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR40## wherein R27 and R28 are as previously defined.
In reaction (b) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
The following example teaches the synthesis of a representative compound of Embodiment C of this invention.
EXAMPLE 1-C 2-(2'-Cyanobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione ##STR41##
2-Cyanobenzoyl chloride (3.9 g, 24 mmol) and 4,4-dimethyl-1,3-cyclohexanedione (3.3 g, 24 mmol) were dissolved in 75 ml methylene chloride. Triethylamine (5.0 ml, 36 mmol) was added dropwise and the resulting solution stirred for one and one-half hours at room temperature. The solution was washed with water, 2 normal hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K2 CO3) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (4.4 ml, 32 mmol) and acetone cyanohydrin (5 drops) were added and the solution stirred for two hours. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K2 CO3. The aqueous extract was acidified with concentrated hydrochloric acid and extracted with ether. The ether was washed with water and brine, dried (MgSO4) and concentrated under vacuum. The residue was purified by silica gel chromatography, yielding 1.2 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
The compounds of Embodiments D and D' of the present invention can be prepared by the following two-step general method.
The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR42## wherein R31 through R38 and moderate base are as defined and X is halogen, preferably chlorine, C1 -C4 alkyl-C(O)--O--, C1 -C4 alkoxy-C(O)--O-- or ##STR43## wherein R37 and R38 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C1 -C6 alkylamine, alkali metal carbonate or alkali metal phosphate.
Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR44## wherein the moderate base and R31 through R38 are as defined above.
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.
The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C2 -C5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the cyanide source, the rearrangementt may be conducted at temperatures up to about 50° C.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR45## wherein R37 and R38 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods described therein. ##STR46## wherein R37 and R38 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR47## wherein R37 and R38 are as previously defined.
In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR48## wherein R37 and R38 are as previously defined.
In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
The following examples teach the synthesis of representative compounds of Embodiment D and D' of this invention.
EXAMPLE 1-D,D' 2-(2'-Nitrobenzoyl)-1,3-cyclohexanedione ##STR49##
2-Nitrobenzoyl chloride (5.0 g, 27 mmol) and cyclohexanedione (3.0 g, 27 mmol) were dissolved in methylene chloride. Triethylamine (4.9 ml, 35 mmol) was added dropwise and the resulting solution stirred for one hour. The solution was washed with 2 normal hydrochloric acid (2N HCl), water, 5% potassium carbonate solution and saturated sodium chloride solution, dried over anhydrous magnesium sulfate (MgSO4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (1 equivalent) and potassium cyanide (40 mol%) were added and the solution stirred for one hour at room temperature. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% potassium carbonate solution. The aqueous extract was acidified and ether was added. Filtration of the resulting mixture yielded 3.2 g of the desired compound (m.p. 132°-135° C.) which was identified by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
EXAMPLE 2-D,D' 2-(2'-Nitrobenzoyl)-5,5-dimethyl-1,3-cyclohexanedione ##STR50##
Triethylamine (3.4 ml, 25 mmol) was added dropwise to a methylene chloride solution of 2-nitrobenzoyl chloride (3.5 g, 19 mmol) and 5,5-dimethylcyclohexanedione (2.4 g, 19 mmol). After stirring for one hour at room temperature an additional 3 equivalents of triethylamine and 0.4 ml acetone cyanohydrin were added. The solution was stirred for 2.5 hours, then washed with 2N HCl and extracted with 5% potassium carbonate solution. The basic extracts were acidified with 2N HCl and extracted with ether. The ether portion was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under vacuum. The residue was recrystallized from ethyl acetate yielding 2.0 g of the desired compound (m.p. 130°-133° C.) which was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
The compounds of Embodiments E and E' of the present invention can be prepared by the following two or three step general method.
The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR51## wherein moderate base, and R40 through R48 are defined herein, and X is halogen, preferably chlorine, C1 -C4 alkyl-C(O)--O--, C1 -C4 alkoxy-C(O)--O-- or ##STR52## wherein R40, R47 and R48 in this portion of the moledule are identical with those in the reactant shown above, and the moderate base is as defined, preferably tri-C1 -C6 alkylamine, alkali metal carbonate or alkali metal phosphate.
Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR53##
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.
The terms "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C2 -C5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C. ##STR54## wherein n is 1 or 2.
Generally in step (3), a mole of the reaction product of step (2) is reacted with a slight mole or two mole excess of of an oxidizing agent such as m-chloroperbenzoic acid after being dissolved in a solvent such as methylene chloride. After completion of the reaction, the resulting mixture is stripped under vacuum. The residue is purified by silica gel chromatography to yield the desired product.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR55## wherein R40, R47 and R48 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods described therein. ##STR56## wherein R40, R47 and R48 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR57## wherein R40, R47 and R48 are as previously defined.
In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR58## wherein R40, R47 and R48 are as defined and X is chlorine, bromine or iodine.
In reaction (c) the substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.
The following examples teach the synthesis representative compounds of Embodiments E and E' of this invention.
EXAMPLE 1-E,E' 2-(2'-Methylthiobenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR59##
2-Methylthiobenzoyl chloride (7.2 g, 39 mmol) and 4,4,6-trimethylcyclohexanedione (5.0 g, 39 mmol) were dissolved in methylene chloride. Triethylamine (7.0 ml, 50 mmol) was added dropwise and the resulting solution stirred for one hour at room temperature. The solution was washed with 2 normal hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K2 CO3) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (2.5 equivalents) and acetone cyanohydrin (0.4 ml) were added and the solution stirred for 45 minutes at room temperature. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K2 CO3. The aqueous extract was acidified with hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO4) and concentrated under vacuum. The residue was purified by trituration with ether, yielding 5.0 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy (nmr), infrared spectroscopy (ir) and mass spectroscopy (ms).
EXAMPLE 2-E,E' 2-(2'-Methanesulfonylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR60##
The benzoyl cyclohexanedione prepared in Example 1 (2.5 g, 7.9 mmol) was dissolved in 40 ml methylene chloride. m-Chloroperbenzoic acid (3.5 g, 16 mmol) was added and the resulting solution was stirred for 45 minutes. The solution was concentrated under vacuum. Purification of the residue by silica gel chromatography yielded 1.7 g of a viscous oil which was identified as the desired compound by nmr, ir and ms.
EXAMPLE 3-E,E' 2-(4'-Trifluoromethyl-2'-methanesulfinylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione ##STR61##
2-(4'-Trifluoromethyl-2'-methylthiobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione (5.0 g, 14 mmol) (which was prepared according to the method of Example 1) was dissolved in 50 ml methylene chloride. A solution of m-chloroperbenzoic acid (2.4 g.-80%, 14 mmol) in 50 ml methylene chloride was added dropwise and the resulting solution was stirred for three hours at room temperature. After concentration under vacuum, the residue was dissolved in ether and washed with 1% hydrochloric acid. A 5% copper(II) acetate solution was added to the ether fraction, followed by hexane. The liquid phase was decanted and the remaining gummy solid stirred with 6N HCl and ether. The ether layer was dried (MgSO4) and concentrated to give 4.7 of a thick yellow solid. Purification on a centrifugally accelerated thin layer chromatograph (4 mm silica gel, 50:50:1 hexane:ethyl acetate:acetic acid-eluent) yielded 2.4 g of a viscous oil which was identified as the desired compound by nmr, ir and ms.
The compounds of Embodiments F and F' of the present invention can be prepared by the following two-step general method.
The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR62## wherein R50 through R58 are as defined and X is halogen, preferably chlorine, C1 -C4 alkyl-C(O)--O--, C1 -C4 alkoxy-C(O)--O-- or ##STR63## wherei R50, R57 and R58 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C1 -C6 alkylamine, alkali metal carbonate or alkali metal phosphate.
Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete.
The reaction product is worked up by conventional techniques. ##STR64## wherein R50 through R58 are as defined.
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 80° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.
The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C2 -C5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR65## wherein R50, R57 and R58 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are four representative examples of the methods described therein. ##STR66## wherein R50, R57 and R58 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR67## wherein R50, R57 and R58 are as previously defined.
In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR68## wherein R50, R57 and R58 are as defined and X is chlorine, bromine or iodine.
The substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.
The following example teachs the synthesis of a representative compound of Embodiments F and F' of this invention.
EXAMPLE 1-F,F' 2-(4'-Bromo-2'-trifluoromethylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR69##
4-Bromo-2-trifluoromethylbenzoyl chloride (4.3 g, 15 mmol) and 4,4,6-trimethyl-1,3-cyclohexanedione (2.3 g, 15 mmol) were dissolved in 100 ml methylene chloride. The solution was cooled with an ice bath and triethylamine (2.1 ml, 15 mmol) in 10 ml methylene chloride was added dropwise. The ice bath was then removed and the resulting solution stirred for 30 minutes at room temperature. The solution was washed with 2N hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K2 CO3) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO4) and concentrated under vacuum. The residue (5.1 g) was dissolved in 20 ml acetonitrile. Triethylamine (3.5 ml, 25 mmol) and 0.4 ml acetone cyanohydrin were added and the solution stirred for two hours at room temperature while protected by a drying tube (calcium sulfate). After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K2 CO3. The aqueous extract was acidified with concentrated hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO4) and concentrated under vacuum. The resulting oil was purified on a silica gel column (80:20:1 hexane:ethyl acetate: acetic acid-eluent), yielding 1.5 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
The compounds of Embodiment G and G' of the present invention can be prepared by the following two-step general method.
The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR70## wherein R60 through R66 and moderate base are as defined and X is halogen, preferably chlorine, C1 -C4 alkyl-C(O)--O--, C1 -C4 alkoxy-C(O)--O-- or ##STR71## wherein R60, R65 and R66 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C1 -C6 alkylamine alkali metal carbonate or alkali metal phosphate.
Generally, in step (1) mole amounts of the trione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR72## wherein the moderate base and R60 through R66 are defined above.
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangment is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.
The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C2 -C5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the crown ethers.
A number of different solvents are useful in this process, depending on the nature of the acid halide or the acylated porduct. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR73## wherein R60, R65 and R66 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods described therein. ##STR74## wherein R60, R65 and R66 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR75## wherein R60, R65 and R66 are as previously defined.
In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR76## wherein R60, R65 and R66 are as previously defined.
In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
The following example teaches the synthesis of a representative compound of Embodiment G and G' of this invention.
EXAMPLE 1-G,G' 2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione ##STR77##
2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and 4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) were dissolved in methylene chloride. Triethylamine was added and the resulting solution stirred at room temperature for 30 minutes. The solution was washed with 1 normal hydrochloric acid (1N HCl), and saturated sodium chloride (brine), dried over anhydrous magnesium sulfate (MgSO4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetone cyanohydrin (0.5 g, 0.6 equivalent) were added and the mixture stirred at room temperature for 4 hours. After dilution with ether, the solution was washed with 1N HCl and extracted with 5% K2 CO3. The basic extract was acidified with HCl and extracted with ether. The ether extract was washed with brine, dried over MgSO4 and concentrated under vacuum, yielding 2.2 g of crude product. This was recrystallized from benzene to remove syncarpic acid still present. Concentration of the mother liquor under vacuum gave 1.7 g of the desired product as an oil, which solidifed on standing (m.p. 76°-82° C.). It was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
The following are tables of certain selected compounds of Embodiments A-G' that are preparable according to the procedures described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.
                                  TABLE I-A                               
__________________________________________________________________________
 ##STR78##                                                                
Cmpd.                                         n.sub.D.sup.30 or           
No. R         R.sup.1                                                     
                 R.sup.2                                                  
                     R.sup.3    R.sup.4  R.sup.5                          
                                              m.p. °C.             
__________________________________________________________________________
1A  CH.sub.3  CH.sub.3                                                    
                 Cl  H          H        H    1.5613                      
2A  CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-Cl     H    1.5655                      
3A  CH.sub.3  CH.sub.3                                                    
                 Cl  H          H        6-Cl 103-108                     
4A* H         H  Cl  H          4-Cl     H    138-140                     
5A  CH.sub.3  CH.sub.3                                                    
                 Br  H          H        H                                
6A  CH.sub.3  CH.sub.3                                                    
                 Cl  H          H        5-Cl 74-77                       
7A  H         H  Cl  H          H        5-Cl 104-107                     
8A  H         H  Br  H          H        H    93-96                       
9A  H         H  Cl  H          H        H    79-87                       
10A H         H  I   H          H        H    66-70                       
11A H         H  Cl  H          4-NO.sub.2                                
                                         H    118-122                     
12A H         H  Cl  H          H        6-Cl 143-148                     
13A H         H  Cl  H          H        5-Br 109-115                     
14A H         H  I   3-I        H        5-I  164-167                     
15A H         H  Cl  H          H        5-CH.sub.3                       
                                              60-65                       
16A H         H  Cl  H          4-CH.sub.3                                
                                         H    79-86                       
17A H         H  Cl  H          4-CH.sub.3 O                              
                                         H    60-63                       
18A H         H  Cl  3-Cl       H        6-Cl                             
19A H         H  Cl  H          H        5-CH.sub.3 O                     
                                              77-80                       
20A H         H  Cl  3-Cl       H        H    80-90                       
21A H         H  Cl  H          H        5-CF.sub.3                       
                                              74-75                       
22A H         H  Cl  H          H        5-NO.sub.2                       
                                              140-143                     
23A H         H  Cl  3-Cl       4-Cl     H    152-154                     
24A H         H  Cl  3-Cl       4-CH.sub.3 O                              
                                         H    169-170                     
25A H         H  Cl  H          4-Br     H    104-107                     
26A CH.sub.3  CH.sub.3                                                    
                 CH.sub.3 O                                               
                     H          H        H    104-108                     
27A H         H  Cl  H                                                    
                                 ##STR79##                                
                                         H                                
28A H         H  Br  H          H        (a)                              
29A H         H  CH.sub.3 O                                               
                     3-CH.sub.3 O                                         
                                H        H    75-79                       
30A H         H  CH.sub.3 O                                               
                     H          H        5-CH.sub.3 O                     
                                              89-92                       
31A H         H  Br  H          4-CH.sub.3 O                              
                                         5-CH.sub.3 O                     
                                              92-96                       
32A H         H  Br  H          (4)-OCH.sub.2 O-(5)                       
                                              63-68                       
33A CH.sub.3  CH.sub.3                                                    
                 Cl  3-Cl       4-Cl     H    86-89                       
34A H         H  Cl  3-Cl       H        5-Cl                             
35A CH.sub.3  CH.sub.3                                                    
                 Cl  3-Cl       H        5-Cl 105-109                     
36A CH.sub.3  CH.sub.3                                                    
                 Cl  3-Cl       4-Cl     5-Cl 137-139                     
37A H         H  Cl  3-Cl       4-Cl     5-Cl 106-110                     
38A H         H  Cl  H          4-Cl     5-Cl 108-111                     
39A                                                                       
     ##STR80##                                                            
              H  Cl  H          4-Cl     H                                
40A                                                                       
     ##STR81##                                                            
              H  Cl  H          4-Cl     H                                
41A CH(CH.sub.3).sub.2                                                    
              H  Cl  H          4-Cl     H                                
42A CH(CH.sub.3).sub.2                                                    
              H  Cl  3-Cl       4-Cl     H                                
43A H         H  Cl  H          4-F      H                                
44A Sodium salt of Compound No. 23            85-94                       
45A isopropylamine salt of Compound No. 23    160-165                     
46A triethylamine salt of Compound No. 23     82-85                       
47A potassium salt of Compound No. 23         107-106                     
48A triethanolammonium salt of Compound No. 39                            
49A sodium salt of Compound No. 43            60-63                       
50A CH(CH.sub.3).sub.2                                                    
              H  Cl  3-CH.sub.3 O                                         
                                4-Br     H                                
51A H         H  Cl  H          4-CH.sub.3 SO.sub.2                       
                                         H    140-141                     
52A H         CH.sub.3                                                    
                 Cl  H          4-Cl     H                                
53A i-C.sub.4 H.sub.9                                                     
              H  Cl  H          4-Cl     H                                
54A i-C.sub.3 H.sub.7                                                     
              H  Cl  3-CH.sub.3 O                                         
                                H        H                                
55A CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-CH.sub.3 SO.sub.2                       
                                         H                                
56A CH.sub.3  CH.sub.3                                                    
                 Cl  3-CH.sub.3 4-Cl     H                                
57A H         H  Cl  3-CH.sub.3 4-Cl     H    56-64                       
58A H         H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                
                                         H     98-102                     
59A H         H  Cl  3-Cl       4-C.sub.2 H.sub.5 SO.sub.2                
                                         H     98-109                     
60A H         H  Cl  H          4-C.sub.3 H.sub.7 SO.sub.2                
                                         H    semi-solid                  
61A H         H  Cl  3-CH.sub.3 O                                         
                                4-CH.sub.3 SO.sub.2                       
                                         H    48-59                       
62A CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-n-C.sub.3 H.sub.7 SO.sub.2              
                                         H    semi-solid                  
63A H         H  Cl  3-Cl       4-n-C.sub.3 H.sub.7 SO.sub.2              
                                         H      145-148.5                 
64A H         H  Cl  3-C.sub.2 H.sub.5 S                                  
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    oil                         
65A CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    103-108                     
66A CH.sub.3  CH.sub.3                                                    
                 Cl  3-Cl       4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    108-114                     
67A i-C.sub.3 H.sub.7                                                     
              H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    brown gum                   
68A H         H  Cl  3-Cl       4-CH.sub.3 SO.sub.2                       
                                         H    145-154                     
69A i-C.sub.3 H.sub.7                                                     
              H  Cl  3-Cl       4-CH.sub.3 SO.sub.2                       
                                         H                                
70A H         H  Br  H          4-CH.sub.3 SO.sub.2                       
                                         H    brown gum                   
71A H         H  Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2              
                                         H    semi-solid                  
72A H         H  Cl  H          4-CH.sub.3 S                              
                                         H    74-77                       
73A H         H  Cl  3-Cl       4-CH.sub.3 S                              
                                         H                                
74A CH.sub.3  CH.sub.3                                                    
                 Cl  3-Cl       4-n-C.sub.3 H.sub.7 SO.sub.2              
                                         H    120-123                     
75A H         H  Cl  H          4-n-C.sub.4 H.sub.9 SO.sub.2              
                                         H    semi-solid                  
76A CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-n-C.sub.4 H.sub.9 SO.sub.2              
                                         H                                
77A H         H  Cl  3-C.sub.2 H.sub.5 O                                  
                                4-CH.sub.3 SO.sub.2                       
                                         H    semi-solid                  
78A H         H  Cl  3-CH.sub.3 O                                         
                                4-n-C.sub.3 H.sub.7 SO.sub.2              
                                         H    golden gum                  
79A CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2              
                                         H    125-128                     
80A CH(CH.sub.3).sub.2                                                    
              H  CH.sub.3 O                                               
                     3-Cl       5-Cl     H                                
81A H         H  Cl  3-CH.sub.3 O                                         
                                4-Br     H    101-111                     
82A H         H  Cl  3-CH.sub.3 4-Cl     H    56-64                       
83A H         H  Cl  H          4-Cl     5-CH.sub.3 O                     
                                              softens >70                 
84A CH(CH.sub.3).sub.2                                                    
              H  Cl  3-n-C.sub.3 H.sub.7 O                                
                                4-Br     H                                
85A H         H  Cl  3-C.sub.2 H.sub.5 O                                  
                                4-Br     H    101-104                     
86A H         H  Cl  H          4-i-C.sub.4 H.sub.9 SO.sub.2              
                                         H    136-140                     
87A CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-i-C.sub.4 H.sub.9 SO.sub.2              
                                         H                                
88A H         H  Cl  3-Cl       4-i-C.sub.3 H.sub.7 SO.sub.2              
                                         H    173-176                     
89A H         H  Cl  3-Cl       4-n-C.sub.4 H.sub.9 SO.sub.2              
                                         H    135-138                     
90A H         H  Cl  3-C.sub.2 H.sub.5 O                                  
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    gum                         
91A H         H  Cl  3-CH.sub.3 O                                         
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    gum                         
92A H         H  Cl  3-Cl       4-C.sub.2 H.sub.5 S                       
                                         H    91-94                       
93A H         H  Cl  3-C.sub.2 H.sub.5 S                                  
                                4-n-C.sub.3 H.sub.7 SO.sub.2              
                                         H    oil                         
94A H         H  Cl  3-C.sub.2 H.sub.5 S                                  
                                4-C.sub.2 H.sub.5 S                       
                                         H    oil                         
95A H         H  Cl  H          4-(CH.sub.3).sub.2 NSO.sub.2              
                                         H    oil                         
96A H         H  Cl  3-C.sub.2 H.sub.5 O                                  
                                4-n-C.sub.3 H.sub.7 SO.sub.2              
                                         H                                
97A H         H  Cl  3-n-C.sub.3 H.sub.7 O                                
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    oil                         
98A CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-(CH.sub.3).sub.2 NSO.sub.2              
                                         H    oil                         
99A H         H  Cl  H          4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2       
                                         H    90-92                       
100A                                                                      
    CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2       
                                         H                                
101A                                                                      
    H         H  Cl  H          4-C.sub.2 H.sub.5 S                       
                                         H                                
102A                                                                      
    H         H  Cl  H          4-n-C.sub.3 H.sub.7 S                     
                                         H                                
103A                                                                      
    H         H  Cl  H          4-i-C.sub.3 H.sub.7 S                     
                                         H                                
104A                                                                      
    H         H  Cl  H          4-C.sub.2 H.sub.5 SO                      
                                         H                                
105A                                                                      
    H         H  CH.sub.3 O                                               
                     H          4-NO.sub.2                                
                                         H    semi-solid                  
106A                                                                      
    H         H  Cl  3-n-C.sub.3 H.sub.7 O                                
                                4-Br     H                                
107A                                                                      
    H         H  Cl  3-n-C.sub.3 H.sub.7 O                                
                                4-CH.sub.3 SO.sub.2                       
                                         H     96-100                     
108A                                                                      
    H         H  Cl  3-allyloxy 4-CH.sub.3 SO.sub.2                       
                                         H    semi-solid                  
109A                                                                      
    H         H  Cl  3-CH.sub.3 C(O)NH                                    
                                4-Cl     H    155-160                     
110A                                                                      
    H         H  Cl  3-Cl       4-n-C.sub.3 H.sub.7 S                     
                                         H                                
111A                                                                      
    H         H  Cl  3-CH.sub.3 O                                         
                                4-NO.sub.2                                
                                         H    150-153                     
112A                                                                      
    H         H  Cl  3-allyloxy 4-C.sub.2 H.sub.5 SO.sub.2                
                                         H                                
113A                                                                      
    H         H  Cl  3-CH.sub.2 BrCHBrCH.sub.2 O                          
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H                                
114A                                                                      
    H         H  Cl  3-n-C.sub.4 H.sub.9 O                                
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    gum                         
115A                                                                      
    H         H  Cl  3-i-C.sub.4 H.sub.9 O                                
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H                                
116A                                                                      
    H         H  Cl  H          4-allylthio                               
                                         H                                
117A                                                                      
    CH.sub.3  CH.sub.3                                                    
                 Cl  H          4-NO.sub.2                                
                                         H                                
118A                                                                      
    H         H  Cl  3-CH.sub.3 C(O)N(CH.sub.3)                           
                                4-Cl     H                                
119A                                                                      
    H         H  Cl  3-i-C.sub.3 H.sub.7 O                                
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H                                
120A                                                                      
    H         H  Cl  3-CH.sub.2 ClCH.sub.2 CH.sub.2 O                     
                                4-C.sub.2 H.sub.5 SO.sub.2                
                                         H    gum                         
121A                                                                      
    H         H  Cl  H          4-t-C.sub.4 H.sub.9 S                     
                                         H                                
122A                                                                      
    H         H  Cl  3-CH.sub.3 O                                         
                                4-CH.sub.2 H.sub.5 S                      
                                         H                                
123A                                                                      
    H         H  Cl  H          4-CF.sub.3                                
                                         H                                
124A                                                                      
    H         H  Cl  H          4-Cl     6-Cl                             
125A                                                                      
    H         H  Cl  3-CH.sub.3 C(O)N(CH.sub.3)                           
                                H        H    131-135                     
126A                                                                      
    H         H  Cl  3-CH.sub.3 C(O)NH                                    
                                H        H                                
127A                                                                      
    H         H  Cl  3-(CH.sub.3).sub.2 N                                 
                                4-Cl     H                                
128A                                                                      
    CH.sub.3  H  Cl  3-CH.sub.3 O                                         
                                4-CH.sub.3 SO.sub.2                       
                                         H    117-122                     
129A                                                                      
    H         H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                
                                         H                                
130A                                                                      
    H         H  Br  H          H        H                                
131A                                                                      
    H         H  Br  H          4-C.sub.2 H.sub.5 OC(O)                   
                                         H                                
132A                                                                      
    H         H  Cl  H          4-CN     H    183-184                     
133A                                                                      
    H         H  Cl  3-CH.sub.3 C(O)NH                                    
                                H        6-NO.sub.2                       
134A                                                                      
    H         H  Cl  3-(CH.sub.3).sub.2 N                                 
                                H        H                                
135A                                                                      
    H         H  Cl  3-Cl       4-ClCH.sub.2 CH.sub.2 SO.sub.2            
                                         H                                
__________________________________________________________________________
 *Prepared in Exampel 1A.                                                 
 ##STR82##                                                                

                                  TABLE I-B                               
__________________________________________________________________________
 ##STR83##                                                                
Compound                                                                  
Number                                                                    
      R.sup.10 R.sup.11                                                   
                   R.sup.12                                               
                       R.sup.13                                           
                             R.sup.14  R.sup.15                           
                                          R.sup.16                        
                                             R.sup.17                     
                                                R.sup.18                  
__________________________________________________________________________
 1B                                                                       
       ##STR84##                                                          
               H   Cl  H     4-Cl      H  H  H  H                         
 2B                                                                       
       ##STR85##                                                          
               CH.sub.3                                                   
                   Cl  H     4-Cl      H  H  H  H                         
 3B   triethanolammonium salt of Compound No. 2                           
 4B   triethanolammonium salt of Compound No. 7                           
 5B                                                                       
       ##STR86##                                                          
               CH.sub.3                                                   
                   Cl  3-Cl  4-Cl      H  H  H  H                         
 6B   triethanolammonium salt of compound No. 5                           
 7B.sup.a                                                                 
      CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-Cl      H  H  H  H                         
 8B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-Cl      CH.sub.3                           
                                          H  H  H                         
 9B   CH.sub.3 n-C.sub.3 H.sub.7                                          
                   Cl  H     4-Cl      H  H  H  H                         
10B   CH.sub.3 H   Cl  H     4-Cl      H  H  H  H                         
11B   CH.sub.3 H   Cl  H     4-Cl      CH.sub.3                           
                                          H  H  H                         
12B   C.sub.5 H.sub.10                                                    
                   Cl  H     4-Cl      H  H  H  H                         
13B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-Cl      H  H  H  H                         
14B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-Cl      CH.sub.3                           
                                          H  H  H                         
15B   i-C.sub.3 H.sub.7                                                   
               H   Cl  3-Cl  4-Cl      H  H  H  H                         
16B   CH.sub.3 CH.sub. 3                                                  
                   Cl  H     4-CH.sub.3 SO.sub.2                          
                                       H  H  H  H                         
17B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-CH.sub.3 SO.sub.2                          
                                       CH.sub.3                           
                                          H  H  H                         
18B   CH.sub.3 H   Cl  H     4-CH.sub.3 SO.sub.2                          
                                       H  H  H  H                         
19B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-CH.sub.3 SO.sub.2                          
                                       H  H  H  H                         
20B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
21B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
22B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                   
                                       CH.sub.3                           
                                          H  H  H                         
23B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-OCH.sub.3                                        
                             4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
24B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-OCH.sub.3                                        
                             4-CH.sub.3 SO.sub.2                          
                                       H  H  H  H                         
25B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-CH.sub.3                                         
                             4-Cl      H  H  H  H                         
26B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-OCH.sub.3                                        
                             4-Cl      H  H  H  H                         
27B   CH.sub.3 C.sub.2 H.sub.5                                            
                   Cl  H     4-Cl      H  H  H  H                         
28B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     H         H  H  H  H                         
29B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-OCH.sub.3                                        
                             4-Br      H  H  H  H                         
30B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-Br      H  H  H  H                         
31B   CH.sub.3 C.sub.2 H.sub.5                                            
                   Cl  3-Cl  4-Cl      H  H  H  H                         
32B   n-C.sub.3 H.sub.7                                                   
               H   Cl  H     4-Cl      H  H  H  H                         
33B                                                                       
       ##STR87##                                                          
               n-C.sub.3 H.sub.7                                          
                   Cl  H     4-Cl      H  H  H  H                         
34B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-i-C.sub.3 H.sub.7 SO.sub.2                 
                                       H  H  H  H                         
35B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-i-C.sub.3 H.sub.7 O                              
                             4-Br      H  H  H  H                         
36B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     6-F       H  H  H  H                         
37B   i-C.sub.3 H.sub.7                                                   
               H   Cl  3-Cl  4-Cl      H  H  H  H                         
38B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-OC.sub.2 H.sub.5                                 
                             4-Br      CH.sub.3                           
                                          H  H  H                         
39B   i-C.sub.3 H.sub.7 OC(O)                                             
               H   Cl  H     4-Cl      H  H  H  H                         
40B   C.sub.2 H.sub.5 OC(O)                                               
               n-C.sub.3 H.sub.7                                          
                   Cl  H     4-Cl      H  H  H  H                         
41B   C.sub.5 H.sub.10                                                    
                   Cl  H     4-Cl      H  H  H  H                         
42B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-Cl      H  H  CH.sub.3                     
                                                H                         
43B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                 
                                       H  H  H  H                         
44B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-n-C.sub.3 H.sub.7 SO.sub.2                 
                                       H  H  H  H                         
45B   CH.sub.3 CH.sub.3                                                   
                   CH.sub.3 O                                             
                       3-CH.sub.3 O                                       
                             H         H  H  H  H                         
46B   CH.sub.3 CH.sub.3                                                   
                   CH.sub.3 O                                             
                       H     4-Cl      H  H  H  H                         
47B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-Br      CH.sub.3                           
                                          H  H  H                         
48B   CH.sub.3 CH.sub.3                                                   
                   Br  H     H         H  H  H  H                         
49B   CH.sub.3 CH.sub.3                                                   
                   I   H     H         H  H  H  H                         
50B   CH.sub.3 CH.sub.3                                                   
                   F   H     H         H  H  H  H                         
51B   CH.sub.3 CH.sub.3                                                   
                   CH.sub.3 O                                             
                       H     H         H  H  H  H                         
52B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-allyoxy                                          
                             4-Br      H  H  H  H                         
53B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-CH.sub.3 SO.sub.2                          
                                       H  H  CH.sub.3                     
                                                H                         
54B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-CH.sub.3 O                                       
                             4-Br      CH.sub.3                           
                                          H  H  H                         
55B   CH.sub.3 CH.sub.3                                                   
                   Br  H     4-CN      H  H  H  H                         
56B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4N(CH.sub.3)SO.sub.2 CF.sub.3                
                                       H  H  H  H                         
57B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-NO.sub.2                                         
                             H         H  H  H  H                         
58B   CH.sub.3 CH.sub.3                                                   
                   C.sub.2 H.sub.5 O                                      
                       H     4-Cl      H  H  H  H                         
59B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-i-C.sub.4 H.sub.9 SO.sub.2                 
                                       H  H  H  H                         
60B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5 O                                
                             4-CH.sub.3 SO.sub.2                          
                                       H  H  H  H                         
61B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-CH.sub.3 O                                       
                             4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
62B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-n-C.sub.4 H.sub.9 SO.sub.2                 
                                       H  H  H  H                         
63B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-n-C.sub.4 H.sub.9 SO.sub.2                 
                                       CH.sub.3                           
                                          H  H  H                         
64B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                   
                                       CH.sub.3                           
                                          H  H  H                         
65B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-F       H  H  H  H                         
66B   CH.sub.3 H   Cl  3-CH.sub.3 O                                       
                             4-Br      H  H  H  H                         
67B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-CH.sub.3 O                                       
                             H         H  H  H  H                         
68B   CH.sub. 3                                                           
               CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5 S                                
                             4-n-C.sub.3 H.sub.7 SO.sub.2                 
                                       H  H  H  H                         
69B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5 S                                
                             4-C.sub.2 H.sub.5 S                          
                                       H  H  H  H                         
70B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5                                  
                             4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
71B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5 S                                
                             4-CH.sub.3 SO.sub.2                          
                                       H  H  H  H                         
72B   CH.sub.3 CH.sub.3                                                   
                   Cl  Cl    4-i-C.sub.3 H.sub.7 SO.sub.2                 
                                       H  H  H  H                         
73B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-n-C.sub.4 H.sub.9 SO.sub.2                 
                                       H  H  H  H                         
74B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5 O                                
                             4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
75B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5 O                                
                             4-Br      H  H  H  H                         
76B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5 O                                
                             4-n-C.sub.3 H.sub.7 SO.sub.2                 
                                       H  H  H  H                         
77B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-n-C.sub.3 H.sub.7 O                              
                             4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
78B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-(CH.sub.3 ).sub.2 NSO.sub.2                
                                       H  H  H  H                         
79B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-CH.sub.3 S                                       
                             4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
80B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-C.sub.2 H.sub.5 S                          
                                       H  H  H  H                         
81B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-C.sub.2 H.sub.5 S                          
                                       H  H  H  H                         
82B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2          
                                       H  H  H  H                         
83B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                 
                                       H  H  H  H                         
84B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-n-C.sub.3 H.sub.7 S                        
                                       CH.sub.3                           
                                          H  H  H                         
85B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-C.sub.2 H.sub.5 S(O)                       
                                       H  H  H  H                         
86B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-i-C.sub.3 H.sub.7 S                        
                                       H  H  H  H                         
87B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-n-C.sub.3 H.sub.7 S                        
                                       H  H  H  H                         
88B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-t-C.sub.4 H.sub.9 SO.sub.2                 
                                       H  H  H  H                         
89B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-i-C.sub.3 H.sub.7 S                        
                                       CH.sub.3                           
                                          H  H  H                         
90B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                 
                                       CH.sub.3                           
                                          H  H  H                         
91B   CH.sub.3 CH.sub.3                                                   
                   Cl  *     4-Cl      H  H  H  H                         
92B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-CH.sub.2CHCH.sub.2 S                       
                                       H  H  H  H                         
93B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-C.sub.2 H.sub.5 O                                
                             4-C.sub.2 H.sub.5 S                          
                                       H  H  H  H                         
94B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-CH.sub.3 S                                 
                                       CH.sub.3                           
                                          H  H  H                         
95B   CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-CH.sub.3 S                                 
                                       H  H  H  H                         
96B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-i-C.sub.3 H.sub.7 O                              
                             4-C.sub.2 H.sub.5 SO.sub.2                   
                                       H  H  H  H                         
97B   CH.sub.3 CH.sub.3                                                   
                   Cl  3-CH.sub.3 O                                       
                             4-C.sub.2 H.sub.5 S                          
                                       H  H  H  H                         
98B   CH.sub.3 CH.sub.3                                                   
                   Cl  **    4-Cl      H  H  H  H                         
99B   CH.sub.3 CH.sub.3                                                   
                   Cl  **    H         H  H  H  H                         
100B  CH.sub.3 CH.sub.3                                                   
                   Cl  3-Cl  4-CH.sub.3 S                                 
                                       H  H  H  H                         
101B  CH.sub.3 CH.sub.3                                                   
                   CH.sub.3 O                                             
                       H     4-NO.sub.2                                   
                                       H  H  H  H                         
102B  CH.sub.3 CH.sub.3                                                   
                   CH.sub.3 O                                             
                       H     4-CF.sub.3                                   
                                       H  H  H  H                         
103B  CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-n-C.sub.3 H.sub.7 SO                       
                                       H  H  H  H                         
104B  CH.sub.3 CH.sub.3                                                   
                   Cl  H     4-n-C.sub.3 H.sub.7 SO                       
                                       CH.sub.3                           
                                          H  H  H                         
__________________________________________________________________________
 .sup.a Prepared in Example IB.                                           
 * = 3CH.sub.3 C(O)NH                                                     
 ** = 3CH.sub.3 C(O)N(CH.sub.3)
The following additional compounds can be prepared by the general method hereinbefore taught.
                                  TABLE I-B                               
__________________________________________________________________________
 ##STR88##                                                                
R.sup.10                                                                  
     R.sup.11                                                             
          R.sup.12                                                        
              R.sup.13                                                    
                    R.sup.14                                              
                           R.sup.15                                       
                              R.sup.16                                    
                                 R.sup.17                                 
                                    R.sup.18                              
__________________________________________________________________________
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  H     4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  H     4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  H     4-Cl   CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  H     4-Cl   H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  H     4-Cl   CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  H     4-Cl   H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  H     4-Cl   CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  H     4-Cl   H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  H     4-Cl   CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  H     4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-Cl  4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-Cl  4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-Cl  4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-Cl  4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-Cl  4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-Cl  4-Cl   CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-Cl  4-Cl   H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-Cl  4-Cl   CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-Cl  4-Cl   H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-Cl  4-Cl   CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-Cl  4-Cl   H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-Cl  4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  H     4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  H     4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  H     4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  H     4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  H     4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  H     4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  H     4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  H     4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  H     4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  H     4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  H     4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  H     4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  H     4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-Cl  4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-OCH.sub.3                                                 
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub. 3                                                                 
     n-C.sub.4 H.sub.9                                                    
          Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-CH.sub.3                                                  
                    4-C.sub.2 H.sub.5 SO.sub.2                            
                           H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-CH.sub.3                                                  
                    4-C.sub. 2 H.sub.5 SO.sub.2                           
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-OCH.sub.3                                                 
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-CH.sub.3                                                  
                    4-CH.sub.3 SO.sub.2                                   
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-CH.sub.3                                                  
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-CH.sub.3                                                  
                    4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-CH.sub.3                                                  
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-CH.sub.3                                                  
                    4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-CH.sub.3                                                  
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-CH.sub.3                                                  
                    4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-CH.sub.3                                                  
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-CH.sub.3                                                  
                    4-Cl   H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-CH.sub.3                                                  
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-Cl   H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-Cl   H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-CH.sub.3                                                  
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-CH.sub.3                                                  
                    4-Cl   H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-CH.sub.3                                                  
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-OCH.sub.3                                                 
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-OCH.sub.3                                                 
                    4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.3 H.sub.7                                                    
          Cl  3-OCH.sub.3                                                 
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-OCH.sub.3                                                 
                    4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     n-C.sub.4 H.sub.9                                                    
          Cl  3-OCH.sub.3                                                 
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-OCH.sub.3                                                 
                    4-Cl   H  H  H  H                                     
CH.sub.3                                                                  
     H    Cl  3-OCH.sub.3                                                 
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-OCH.sub.3                                                 
                    4-Cl   H  H  H  H                                     
C.sub.2 H.sub.5                                                           
     H    Cl  3-OCH.sub.3                                                 
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-Cl   H  H  H  H                                     
n-C.sub.4 H.sub.9                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-Cl   H  H  H  H                                     
i-C.sub.3 H.sub.7                                                         
     H    Cl  3-OCH.sub.3                                                 
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-OCH.sub.3                                                 
                    4-Cl   H  H  H  H                                     
C.sub.5 H.sub.10                                                          
          Cl  3-OCH.sub.3                                                 
                    4-Cl   CH.sub.3                                       
                              H  H  H                                     
 CH.sub.3                                                                 
     CH.sub.3                                                             
          Cl  3-n-C.sub.3 H.sub.7 O                                       
                    4-Br   H  H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                            
                           CH.sub.3                                       
                              H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  H     4-NO.sub.2                                            
                           H  H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-C.sub.2 H.sub.5 O                                         
                    4-CH.sub.3 S                                          
                           H  H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  H     4-CN   H  H  H  H                                     
CH.sub.3                                                                  
     CH.sub.3                                                             
          Cl  3-(CH.sub.3).sub.2 N                                        
                    4-Cl   H  H  H  H                                     
__________________________________________________________________________

                                  TABLE I-C                               
__________________________________________________________________________
 ##STR89##                                                                
Comp.                                                                     
No.  R.sup.21                                                             
        R.sup.22                                                          
           R.sup.23                                                       
              R.sup.24                                                    
                  R.sup.25                                                
                      R.sup.26                                            
                         R.sup.27                                         
                            R.sup.28                                      
                               n.sub.D.sup.30 or m.p.                     
__________________________________________________________________________
1C.sup.a                                                                  
     CH.sub.3                                                             
        CH.sub.3                                                          
           H  H   H   H  H  H  oil                                        
2C   H  H  H  H   H   H  H  CN 124-140° C.                         
__________________________________________________________________________
 .sup.a Prepared in Example IC.                                           

                                  TABLE I-D                               
__________________________________________________________________________
 ##STR90##                                                                
Comp.                                                                     
No. R.sup.31                                                              
       R.sup.32                                                           
           R.sup.33                                                       
               R.sup.34                                                   
                  R.sup.35                                                
                     R.sup.36                                             
                        R.sup.37                                          
                             R.sup.38 n.sub.D.sup.30 or                   
__________________________________________________________________________
                                      m.p.                                
1D  CH.sub.3                                                              
       H   H   H  H  H  H    H        viscous oil                         
2D  CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  CH.sub.3                                                
                     H  H    H        viscous oil                         
3D.sup.a                                                                  
    H  H   H   H  H  H  H    H        132-135                             
4D  CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    H        viscous oil                         
5D.sup.b                                                                  
    H  H   CH.sub.3                                                       
               CH.sub.3                                                   
                  H  H  H    H        130-133                             
6D  CH.sub.3                                                              
       H   H   H  CH.sub.3                                                
                     H  H    H        viscous oil                         
7D  CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    CF.sub.3 52-61                               
8D  H  H   H   H  H  H  H    CF.sub.3 88-94                               
9D  H  H   CH.sub.3                                                       
               CH.sub.3                                                   
                  H  H  H    CF.sub.3 89-97                               
10D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  3-CH.sub.3                                        
                             H        119-122                             
11D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  3-Cl H        72-79                               
12D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    Cl       118-121                             
13D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  4-Cl H        118-120                             
14D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  5-F  H        130-133                             
15D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  3-CH.sub.3 O                                      
                             H        139-142                             
16D CH.sub.3                                                              
       CH.sub.3                                                           
           CH.sub.3                                                       
               H  H  H  H    CF.sub.3 viscous oil                         
17D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    NO.sub.2 viscous oil                         
18D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    Br       viscous oil                         
19D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  CH.sub.3                                             
                        5-CH.sub.3                                        
                             H        viscous oil                         
20D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  5-CH.sub.3                                        
                             H        viscous oil                         
21D H  H   H   H  H  H  H    F        123-128                             
22D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    F        viscous oil                         
23D H  H   H   H  H  H  H    Cl       viscous oil                         
24D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SO.sub.2 CH.sub.3                            
                                      130-133                             
25D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                  
                                      viscous oil                         
26D H  H   H   H  H  H  H    SO.sub.2 CH.sub.3                            
                                      157-159                             
27D H  H   H   H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                  
                                      120-123                             
28D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  5-F  H        165-195                             
29D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SO.sub.2C.sub.2 H.sub.5                      
                                      oil                                 
30D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  CH.sub.3                                                
                     H  H    SO.sub.2CH.sub.3                             
                                      gum                                 
31D CH.sub.3                                                              
       n-C.sub.4 H.sub.9                                                  
           H   H  H  H  H    H        viscous oil                         
32D H  H   i-C.sub.4 H.sub.9                                              
               H  H  H  H    H        viscous oil                         
33D H  H   H   H  H  H  H    SO.sub.2C.sub.2 H.sub.5                      
                                      viscous oil                         
34D H  H   H   H  H  H  H    CN       viscous oil                         
35D H  H   H   H  H  H  H    SO.sub.2 N(CH.sub.3).sub.2                   
                                      158-159                             
36D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SO.sub.2 N(CH.sub.3).sub.2                   
                                      120-130                             
37D H  H   H   H  H  H  H    SO.sub.2 N(C.sub.2 H.sub.5).sub.2            
                                      158-163                             
38D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SO.sub.2 N(C.sub.2 H.sub.5).sub.2            
                                      oil                                 
39D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H                                                 
                              ##STR91##                                   
                                      oil                                 
40D H  H   CH.sub.3                                                       
               CH.sub.3                                                   
                  H  H  H    SO.sub.2N(C.sub.2 H.sub.5).sub.2             
                                      oil                                 
41D H  H   H   H  H  H  H    SC.sub.2 H.sub.5                             
                                      oil                                 
42D H  H   H   H  H  H  H    S(O)-n-C.sub.3 H.sub.7                       
                                      oil                                 
43D H  H   H   H  H  H  H    S-n-C.sub.3 H.sub.7                          
                                      oil                                 
44D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  CH.sub.3                                                
                     H  H    S-n-C.sub.3 H.sub.7                          
                                      oil                                 
45D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    S-n-C.sub.3 H.sub.7                          
                                      oil                                 
46D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  CH.sub.3                                                
                     H  H    SC.sub.2 H.sub.5                             
                                      oil                                 
47D CH.sub.3                                                              
       CH.sub. 3                                                          
           H   H  H  H  H    SC.sub.2 H.sub.5                             
                                      oil                                 
47D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SC.sub.2 H.sub.5                             
                                      oil                                 
48D H  H   H   H  H  H  H    SCH.sub.3                                    
                                      94-97                               
49D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  CH.sub.3                                                
                     H  H    CF.sub.3 oil                                 
50D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SCH.sub.3                                    
                                      oil                                 
51D c  H   i-C.sub.3 H.sub.7                                              
               H  H  H  H    H        145-148                             
52D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  5-CH.sub.3 O                                      
                             Br       oil                                 
53D H  H   CH.sub.3                                                       
               CH.sub.3                                                   
                  H  H  H    Cl       oil                                 
54D H  H   H   H  H  H  3-CH.sub.3 O                                      
                             Cl       oil                                 
55D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  3-CH.sub.3 O                                      
                             Cl       oil                                 
56D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  CH.sub.3                                                
                     H  H    CH.sub.3 S                                   
                                      oil                                 
57D H  H   H   H  H  H  H                                                 
                              ##STR92##                                   
                                      120-125                             
58D H  H   CH.sub.3                                                       
               CH.sub.3                                                   
                  H  H  H    CN       175-177                             
59D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    CN       151-153                             
60D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  CH.sub.3                                                
                     H  H    CN       oil                                 
61D c  H   H   H  H  H  H    H        oil                                 
62D d  H   H   H  H  H  H    H        oil                                 
63D H  H   CH.sub.3                                                       
               H  H  H  H    Cl       110-115                             
64D H  H   CH.sub.3                                                       
               H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                  
                                      oil                                 
65D d  CH.sub.3                                                           
           H   H  H  H  H    Cl       oil                                 
66D H  H   H   H  H  H  H    SO.sub.2 CHCl.sub.2                          
                                      oil                                 
67D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SO.sub.2 CHCl.sub.2                          
                                      oil                                 
68D H  H   H   H  H  H  c    Br       oil                                 
69D H  H   H   H  H  H  H    SO.sub.2 CH.sub.2 Cl                         
                                      oil                                 
70D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  H  H  H    SO.sub.2 CH.sub.2 Cl                         
                                      wax                                 
71D d  CH.sub.3                                                           
           H   H  H  H  H    H        oil                                 
72D H  H   H   H  H  H  C.sub.2 H.sub.5 O                                 
                             Cl       oil                                 
73D CH.sub.3                                                              
       CH.sub.3                                                           
           H   H  CH.sub.3                                                
                     H  CH.sub.3 O                                        
                             CF.sub.3 oil                                 
__________________________________________________________________________
 .sup.a Prepared in Example 1D,D'.                                        
 .sup.b Prepared in Example 2D,D'.                                        
 .sup. c = C.sub.2 H.sub.5 OC(O)-                                         
 .sup.d = iC.sub.3 H.sub.7 OC(O)-                                         

                                  TABLE I-E                               
__________________________________________________________________________
 ##STR93##                                                                
Comp.                                                                     
No. n R.sup.40                                                            
         R.sup.41                                                         
            R.sup.42                                                      
               R.sup.43                                                   
                  R.sup.44                                                
                     R.sup.45                                             
                        R.sup.46                                          
                           R.sup.47                                       
                               R.sup.48                                   
                                      m.p.                                
__________________________________________________________________________
1E  0 CH.sub.3                                                            
         H  H  H  H  H  H  H   H      79-81° C.                    
2E  0 CH.sub.3                                                            
         CH.sub.3                                                         
            CH.sub.3                                                      
               H  H  H  H  H   H      oil                                 
3E.sup.a                                                                  
    0 CH.sub.3                                                            
         CH.sub.3                                                         
            CH.sub.3                                                      
               H  H  CH.sub.3                                             
                        H  H   H      oil                                 
4E.sup.b                                                                  
    2 CH.sub.3                                                            
         CH.sub.3                                                         
            CH.sub.3                                                      
               H  H  CH.sub.3                                             
                        H  H   H      oil                                 
5E  0 C.sub.2 H.sub.5                                                     
         CH.sub.3                                                         
            CH.sub. 3                                                     
               H  H  H  H  H   H      oil                                 
6E  2 C.sub.2 H.sub.5                                                     
         CH.sub.3                                                         
            CH.sub.3                                                      
               H  H  H  H  H   H      oil                                 
7E  0 CH.sub.3                                                            
         H  H  H  H  H  H  3-Cl                                           
                               Cl     59-64° C.                    
8E  2 CH.sub.3                                                            
         H  H  H  H  H  H  3-Cl                                           
                               Cl     116-119° C.                  
9E  0 CH.sub.3                                                            
         H  H  H  H  H  H  H   CF.sub.3                                   
                                      102-106° C.                  
10E 2 CH.sub.3                                                            
         H  H  H  H  H  H  H   CF.sub.3                                   
                                      oil                                 
11E 0 CH.sub.3                                                            
         CH.sub.3                                                         
            CH.sub.3                                                      
               H  H  H  H  H   CF.sub.3                                   
                                      49-53° C.                    
12E 2 CH.sub.3                                                            
         CH.sub.3                                                         
            CH.sub.3                                                      
               H  H  H  H  H   CF.sub.3                                   
                                      oil                                 
13E.sup.c                                                                 
    1 CH.sub.3                                                            
         CH.sub.3                                                         
            CH.sub.3                                                      
               H  H  H  H  H   CF.sub.3                                   
                                      oil                                 
14E 0 CH.sub.3                                                            
         H  H  H  H  H  H  3-Cl                                           
                               SCH.sub.3                                  
                                      105-107° C.                  
15E 1 CH.sub.3                                                            
         H  H  H  H  H  H  3-Cl                                           
                               S(O)CH.sub.3                               
                                      oil                                 
16E 0 CH.sub.3                                                            
         H  H  H  H  H  H  H   SO.sub.2 n-C.sub.3 H.sub.7                 
                                      oil                                 
17E 0 CH.sub.3                                                            
         H  H  H  H  H  H  H   SCH.sub.3                                  
                                      101-103° C.                  
18E 2 CH.sub.3                                                            
         H  H  H  H  H  H  H   SO.sub.2 n-C.sub.3 H.sub.7                 
                                      oil                                 
19E 2 CH.sub.3                                                            
         H  H  H  H  H  H  H   SO.sub.2 CH.sub.3                          
                                      194-196° C.                  
20E 0 CH.sub.3                                                            
         H  H  H  H  H  H  3-CH.sub.3                                     
                               H      40-42° C.                    
21E 2 CH.sub.3                                                            
         H  H  H  H  H  H  3-CH.sub.3                                     
                               H      80-86° C.                    
__________________________________________________________________________
 .sup.a Prepared in Example 1E,E'.                                        
 .sup.b Prepared in Example 2E,E'.                                        
 .sup.c Prepared in Example 3E,e'.                                        

                                  TABLE I-F                               
__________________________________________________________________________
 ##STR94##                                                                
Comp.                                 n.sub.D.sup.30                      
No. R.sup.50                                                              
       R.sup.51                                                           
          R.sup.52                                                        
             R.sup.53                                                     
                 R.sup.54                                                 
                    R.sup.55                                              
                       R.sup.56                                           
                          R.sup.57                                        
                              R.sup.58                                    
                                      or m.p.                             
__________________________________________________________________________
1F  CH.sub.3                                                              
       H  H  H   H  H  H  H   H       35-42° C.                    
2F  CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   H       47-53° C.                    
3F  CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   Br      oil                                 
4F  CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   CN      oil                                 
5F  CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  3-NO.sub.2                                      
                              H       oil                                 
6F  CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  5-Cl                                            
                              H       oil                                 
7F  CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   CH.sub.3 SO.sub.2                           
                                      oil                                 
8F  CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  CH.sub.3                                              
                       H  H   CH.sub.3 SO.sub.3                           
                                      oil                                 
9F  CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  3-Cl                                            
                              H       oil                                 
10F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  CH.sub.3                                              
                       H  H   C.sub.2 H.sub.5 SO.sub.2                    
                                      oil                                 
11F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   C.sub.2 H.sub.5 SO.sub.2                    
                                      oil                                 
12F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   n-C.sub.3 H.sub.7 SO.sub.2                  
                                      oil                                 
13F CH.sub.3                                                              
       H  H  H   H  H  H  H   CH.sub.3 SO.sub.2                           
                                      oil                                 
14F CH.sub.3                                                              
       H  H  H   H  H  H  H   n-C.sub.3 H.sub.7 SO.sub.2                  
                                      oil                                 
15F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   CH.sub.3 S                                  
                                      oil                                 
16F C.sub.2 H.sub.5                                                       
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   Br      oil                                 
17F CH.sub.3                                                              
       H  H  H   H  H  H  H   CN      oil                                 
18F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   F       oil                                 
19F CH.sub.3                                                              
       H  H  H   H  H  H  H   C.sub.2 H.sub.5SO.sub.2                     
                                      oil                                 
20F CH.sub.3                                                              
       H  H  H   H  H  H  3-Cl                                            
                              H       65-67° C.                    
21F CH.sub.3                                                              
       H  H  H   H  H  H  3-I H       oil                                 
22F CH.sub.3                                                              
       H  H  H   H  H  H  3-NO.sub.2                                      
                              H       oil                                 
23F CH.sub.3                                                              
       H  H  H   H  H  H  3-CN                                            
                              H       96-101° C.                   
24F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   H       oil                                 
25F CF.sub.3                                                              
       H  H  H   H  H  H  H   H       oil                                 
26F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   Br      oil                                 
27F CF.sub.3                                                              
       H  H  H   H  H  H  H   Cl      82-88° C.                    
28F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   Cl      oil                                 
29F CF.sub.3                                                              
       H  H  H   H  H  H  H   C.sub.2 H.sub.5 S                           
                                      oil                                 
30F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   C.sub.2 H.sub.5 SO.sub.2                    
                                      oil                                 
31F CF.sub. 3                                                             
       H  H  H   H  H  H  H   CN      oil                                 
32F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   CN      oil                                 
33F.sup.a                                                                 
    CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  CH.sub.3                                              
                       H  H   Br      oil                                 
34F CH.sub.3                                                              
       H  H  H   H  H  H  H   CH.sub.3                                    
35F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  3-Cl                                            
                              C.sub.2 H.sub.5 SO.sub.2                    
                                      115-117° C.                  
36F CH.sub.3                                                              
       H  H  H   H  H  H  3-Cl                                            
                              C.sub.2 H.sub.5 SO.sub.2                    
                                      oil                                 
37F CH.sub.3                                                              
       b  b  H   H  H  H  3-CF.sub.3                                      
                              H       oil                                 
38F CH.sub.3                                                              
       c  H  i-C.sub.3 H.sub.7                                            
                 H  H  H  3-NO.sub.2                                      
                              H       88-108° C.                   
39F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  CH.sub.3                                              
                       H  H   CH.sub.3 S                                  
                                      oil                                 
40F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   CH.sub.3 S                                  
                                      oil                                 
41F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  CH.sub.3                                              
                       H  H   CH.sub.3 SO.sub.2                           
                                      oil                                 
42F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   CF.sub.3                                    
                                      oil                                 
43F CH.sub.3                                                              
       H  H  H   H  H  H  H   CF.sub.3                                    
                                      114-120° C.                  
44F CH.sub.3                                                              
       H  H  H   H  H  H  3-Cl                                            
                              Cl      oil                                 
45F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  3-Cl                                            
                              Cl      oil                                 
46F CH.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  3-CF.sub.3                                      
                              H       oil                                 
47F CF.sub.3                                                              
       H  H  H   H  H  H  H   CH.sub.3 S                                  
                                      oil                                 
48F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  CH.sub.3                                              
                       H  H   CF.sub.3                                    
                                      oil                                 
49F CF.sub.3                                                              
       H  H  H   H  H  H  H   CF.sub.3                                    
                                      oil                                 
50F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  H  H  H   CF.sub.3                                    
                                      oil                                 
51F CH.sub.3                                                              
       H  H  CH.sub.3                                                     
                 H  H  H  H   CH.sub.3 SO.sub.2                           
                                      oil                                 
52F CF.sub.3                                                              
       CH.sub.3                                                           
          CH.sub.3                                                        
             H   H  CH.sub.3                                              
                       H  H   C.sub.2 H.sub.5 SO.sub.2                    
                                      oil                                 
53F CH.sub.3                                                              
       H  H  H   H  H  H  H   Br      94-98° C.                    
54F CH.sub.3                                                              
       H  H  H   H  H  H  d   H       oil                                 
__________________________________________________________________________
 .sup.a Prepared in Example 1F,F'.                                        
 .sup.b (CH.sub.2).sub.5                                                  
 .sup.c C.sub.2 H.sub.5 OC(O)-                                            
 .sup.d 3-N(CH.sub.3)COCH.sub.3                                           

                                  TABLE I-G                               
__________________________________________________________________________
 ##STR95##                                                                
Comp.                                                                     
No. R.sup.60                                                              
         R.sup.61                                                         
            R.sup.62                                                      
               R.sup.63                                                   
                  R.sup.64                                                
                     R.sup.65                                             
                          R.sup.66                                        
                                  m.p. °C.                         
__________________________________________________________________________
1G  NO.sub.2                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    H       112-117                                 
2G.sup.(a)                                                                
    NO.sub.2                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-Cl    76-82                                   
3G  Cl   CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SO.sub.2 CH.sub.3                             
                                   176-179°                        
4G  CH.sub.3                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SO.sub.2 C.sub.2 H.sub.5                      
                                  gum                                     
5G  CF.sub.3                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-CF.sub.3                                      
                                  viscous oil                             
6G  NO.sub.2                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SO.sub.2 CH.sub.2 Cl                          
                                  oil                                     
7G  Cl   CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-F     gum                                     
8G  Cl   CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     3-OC.sub.2 H.sub.5                                   
                          4-SO.sub.2 C.sub.2 H.sub.5                      
                                  gum                                     
9G  NO.sub.2                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SO.sub.2 CH.sub.3                             
                                  gum                                     
10G Cl   CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SCH.sub.3                                     
                                  gum                                     
11G CH.sub.3                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     3-NO.sub.2                                           
                          H       gum                                     
12G I    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    H       gum                                     
13G OCH.sub.3                                                             
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-Cl    gum                                     
14G Cl   CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     3-OCH.sub.3                                          
                          4-Br    gum                                     
15G NO.sub.2                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SO.sub.2 nC.sub.3 H.sub.7                     
                                  gum                                     
16G NO.sub.2                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SO.sub.2 N(CH.sub.3).sub.2                    
                                  gum                                     
17G NO.sub.2                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-CN    .sup. 148-150°                   
18G SO.sub.2 CH.sub.3                                                     
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    H       gum                                     
19G NO.sub.2                                                              
         CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-CF.sub.3                                      
                                  gum                                     
20G H    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-Cl    gum                                     
21G H    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SCF.sub.3                                     
                                  gum                                     
22G H    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-OCF.sub.3                                     
                                  gum                                     
23G Cl   CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                      
                                  gum                                     
24G H    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-C(O)CH.sub.3                                  
                                  gum                                     
25G H    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SO.sub.2CH.sub.3                              
                                  129-131                                 
26G H    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-SCH.sub.3                                     
                                  89-92                                   
27G H    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-CF.sub.3                                      
                                  115-125                                 
28G H    CH.sub.3                                                         
            CH.sub.3                                                      
               CH.sub.3                                                   
                  CH.sub.3                                                
                     H    4-CN    87-95                                   
__________________________________________________________________________
 .sup.(a) prepared in Example 1G,G'.
Herbicidal Screening Tests
As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.
Pre-emergence herbicide test.
On the day preceding treatment, seeds of eight different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea), redroot pigweed (PW) (Amaranthus refroflexus) or curly dock (CD) (Rumex crispus), and yellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.
Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).
After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.
The results of the tests are shown in the following Tables
                                  TABLE II-A                              
__________________________________________________________________________
Pre-Emergence Herbicidal Activity                                         
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No. FT  WG WO  AMG VL  MD PW  CD YNS                                      
__________________________________________________________________________
 1A 100 90 20  40  65  50 35     80                                       
 2A 80  90 0   30  80  90 20     90                                       
 3A 0   0  0   40  40  40 0      0                                        
 4A 100 100                                                               
           50  35  100 100                                                
                          90     95                                       
 5A 100 95 65  35  90  85 50     95                                       
 6A 50  25 0   25  100 100                                                
                          35     80                                       
 7A 80  90 10  60  100 100                                                
                          100    80                                       
 8A 95  95 45  40  100 80 95     95                                       
 9A 95  100                                                               
           55  30  100 90 100    95                                       
10A 100 100                                                               
           60  20  85  100                                                
                          100    95                                       
11A 85  100                                                               
           30  40  100 100                                                
                          100    95                                       
12A 85  85 90  75  80  95 90     90                                       
13A 85  75 10  10  85  65 95     90                                       
14A 40  10 80  0   65  40 65     100                                      
15A 40  60 20  30  100 30 75     95                                       
16A 80  80 20  55  75  90 40     95                                       
17A 20  -- 10  25  100 95 85     90                                       
18A 65  -- 30  70  100 100                                                
                          85     90                                       
19A 45  60 0   30  40  0  20     60                                       
20A 30  85 20  40  95  85 40     45                                       
21A 80  100                                                               
           0   80  100 100                                                
                          95     95                                       
22A 20  10 0   20  75  30 45     10                                       
23A 45  95 10  0   100 85 100    95                                       
24A --  100                                                               
           0   25  70  90 --     100                                      
25A --  100                                                               
           25  80  100 100                                                
                          --     100                                      
26A 40  15 0   0   0   10     0  30                                       
27A 40  80 10  20  60  50     30 75                                       
28A 65  75 0   65  100 95     75 55                                       
29A 100 95 55  10  80  75     85 95                                       
30A 20  20 20  10  40  40     50 20                                       
31A 75  95 20  20  100 95     75 10                                       
32A 90  85 20  0   100 85     75 30                                       
33A 80  70 0   40  20  40     90 80                                       
34A 60  40 0   20  95  100    100                                         
                                 60                                       
35A 0   10 0   0   10  20     20 10                                       
36A 0   0  0   20  100 100    100                                         
                                 0                                        
37A 40  0  0   20  100 60     90 --                                       
38A 10  40 0   20  90  80     20 20                                       
39A 80  10 0   0   0   0      0  90                                       
40A 60  0  0   0   0   0      0  90                                       
41A 100 100                                                               
           85  40  95  100    100                                         
                                 100                                      
42A 60  100                                                               
           25  0   0   0      0  25                                       
43A 100 100                                                               
           45  40  80  90     90 100                                      
44A 90  100                                                               
           0   60  100 100    100                                         
                                 95                                       
45A 100 100                                                               
           0   60  100 100    100                                         
                                 100                                      
46A 20  60 0   100 100 100    100                                         
                                 20                                       
47A 60  70 20  100 100 100    100                                         
                                 60                                       
48A 60  0  0   0   0   0      0  40                                       
49A 100 100                                                               
           50  10  60  20     90 100                                      
50A 100 100                                                               
           80  10  60  60     90 100                                      
51A 100 100                                                               
           90  100 100 100    85 100                                      
52A 100 100                                                               
           60  10  100 100    60 100                                      
53A 0   20 0   0   20  20     0  10                                       
54A 10  45 10  0   0   0      0  40                                       
55A 90  100                                                               
           60  100 100 100    90 100                                      
56A 40  70 40  40  40  60     70 50                                       
57A 100 100                                                               
           90  100 100 100    85 100                                      
58A 90  95 0   20  20  40     40 100                                      
59A 95  100                                                               
           85  75  100 100    90 98                                       
60A 95  100                                                               
           50  50  100 100    90 98                                       
61A 100 100                                                               
           75  100 100 100    95 95                                       
62A 100 100                                                               
           95  75  100 100    100                                         
                                 80                                       
63A 100 100                                                               
           40  65  100 100    100                                         
                                 95                                       
64A 100 100                                                               
           98  100 100 100    100                                         
                                 90                                       
65A 100 100                                                               
           80  100 100 100    100                                         
                                 90                                       
66A 100 100                                                               
           75  100 100 100    100                                         
                                 98                                       
73A 100 100                                                               
           60  80  100 100    75 90                                       
74A 100 100                                                               
           70  80  100 100    80 100                                      
75A 70  100                                                               
           0   50  100 100    100                                         
                                 80                                       
76A 40  90 25  10  100 100    100                                         
                                 10                                       
77A 100 100                                                               
           90  100 100 100    85 --                                       
78A 100 100                                                               
           80  100 100 100    90 --                                       
79A 50  100                                                               
           50  50  95  100    100                                         
                                 60                                       
80A 0   0  0   0   0   0      0  0                                        
81A 100 100                                                               
           50  15  100 100    90 100                                      
84A 100 100                                                               
           85  0   0   100    20 100                                      
88A 60  95 35  95  100 100    95 80                                       
89A 75  100                                                               
           40  100 100 100    95 60                                       
90A 100 100                                                               
           90  100 100 100    100                                         
                                 85                                       
105A                                                                      
    80  95 25  0   95  50     70 50                                       
117A                                                                      
    95  100                                                               
           0   25  100 100    50 95                                       
118A                                                                      
    100 100                                                               
           60  100 100 100    100                                         
                                 85                                       
121A                                                                      
    95  100                                                               
           50  75  100 95     100                                         
                                 80                                       
125A                                                                      
    100 100                                                               
           50  80  100 100    100                                         
                                 85                                       
126A                                                                      
    70  100                                                               
           80  80  100 100    100                                         
                                 80                                       
127A                                                                      
    100 100                                                               
           100 100 100 100    -- 80                                       
128A                                                                      
    100 100                                                               
           100 100 100 100    -- 80                                       
129A                                                                      
    100 100                                                               
           95  90  100 100    -- 80                                       
131A                                                                      
    70  85 0   20  95  98     95 90                                       
132A                                                                      
    100 100                                                               
           95  90  100 100    -- 80                                       
133A                                                                      
    100 100                                                               
           100 100 100 100    -- 80                                       
135A                                                                      
    100 100                                                               
           100 80  100 100    -- 80                                       
__________________________________________________________________________

              TABLE II-B                                                  
______________________________________                                    
Pre-Emergence Herbicidal Activity                                         
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No.    FT     WG     WO   AMG   VL   MD   CD   YNS                        
______________________________________                                    
 1B    0      85     10   75    100  80   80   75                         
 2B    90     100    65   100   100  100  100  100                        
 4B    100    100    80   60    100  80   90   100                        
 5B    80     100    20   40    100  100  80   100                        
 6B    40     100    0    40    100  100  80   100                        
 7B    100    100    100  80    100  100  90   100                        
 8B    100    100    60   45    60   60   80   100                        
 9B    60     100    40   20    60   60   60   100                        
10B    100    100    40   5     80   60   80   100                        
11B    100    100    90   10    20   20   40   100                        
12B    0      20     0    0     10   20   10    0                         
13B    100    100    90   40    100  100  100  100                        
15B    90     90     50   20    --   100  100  80                         
16B    100    100    95   100   100  100  90   100                        
17B    100    100    100  100   100  100  100  97                         
18B    100    100    85   100   100  100  90   95                         
19B    100    100    95   100   100  100  100  95                         
20B    100    100    85   100   100  100  100  90                         
21B    100    100    100  100   100  100  100  95                         
22B    100    100    80   100   100  100  100  90                         
25B    100    100    75   80    100  100  100  90                         
26B    100    100    65   30    100  100  100  90                         
27B    20     95     60   5     100  100  90   100                        
28B    100    100    80   20    90   40   80   100                        
29B    100    100    70   20    100  100  100  100                        
30B    100    100    80   60    100  100  80   100                        
31B    80     100    40   10    60   60   80   100                        
32B    20     40     10   0     --   60   100  60                         
33B    0      10     0    0     10   10   0     0                         
34B    100    100    90   80    100  100  90   100                        
35B    100    100    90   40    90   90   90   90                         
36B    100    100    85   0     95   85   95   90                         
37B    90     90     50   20    --   100  100  80                         
39B    15     100    0    50    100  80   70   40                         
40B    0      10     0    0     10   10   0     0                         
41B    0      20     0    0     10   20   10    0                         
42B    100    100    90   45    100  100  65   100                        
43B    100    100    90   100   100  100  100  90                         
44B    100    100    85   100   100  100  100  95                         
45B    65     100    0    0     100  20   20   90                         
46B    100    100    0    20    100  100  98   85                         
47B    100    100    90   85    100  100  100  95                         
48B    100    100    85   15    100  100  85   95                         
49B    100    100    65   0     100  100  50   50                         
50B    80     80     55   0     98   55   80   65                         
51B    95     95     10   0     65   0    25   60                         
52B    100    100    100  100   100  100  100  50                         
53B    100    100    75   100   100  100  100  50                         
54B    100    100    60   15    100  100  100  80                         
55B    100    100    55   15    100  100  90   95                         
56B    100    100    60   20    95   100  90   10                         
57B    5      10     0    0     40   20   0     0                         
58B    10     40     10   10    95   40   100  80                         
59B    100    100    75   80    100  100  100  75                         
60B    100    100    90   100   100  100  85   --                         
61B    100    100    80   100   100  100  100  --                         
62B    95     100    50   95    100  100  85   --                         
63B    100    100    70   100   90   100  100  --                         
64B    100    100    75   100   100  100  85   --                         
65B    100    100    55   40    100  100  90   70                         
66B    100    100    65   35    100  100  100  95                         
67B    100    100    30   15    100  100  95   90                         
71B    100    100    80   100   100  100  80   --                         
72B    100    100    40   100   100  100  90   75                         
73B    90     100    40   100   100  100  95   50                         
74B    100    100    85   95    100  100  90   80                         
75B    100    100    100  70    100  100  100  95                         
77B    100    100    55   40    100  100  90   70                         
81B    90     95     60   10    25   75   90    0                         
82B    40     90     20   35    100  --   75   20                         
91B    100    100    85   100   100  100  80   90                         
101B   85     90     0    0     95   50   50   75                         
______________________________________                                    

              TABLE II-C                                                  
______________________________________                                    
Pre-Emergence Herbicidal Activity                                         
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No.    FT     WG     WO   AMG   VL   MD   CD   YNS                        
______________________________________                                    
1C     65     80     65   55    90   90   35   0                          
______________________________________                                    

              TABLE II-D                                                  
______________________________________                                    
Pre-Emergence Herbicidal Activity                                         
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No.    FT     WG     WO   AMG   VL   MD   CD   YNS                        
______________________________________                                    
 1D    100    100    85   30    100  100  90   90                         
 2D    100    100    100  50    100  100  95   95                         
 3D    100    100    85   25    100  100  100  95                         
 4D    100    100    100  20    100  85   95   90                         
 5D    100    100    45   25    100  100  90   90                         
 6D    100    100    95   40    100  100  85   90                         
 9D    100    100    90   90    100  100  80   90                         
10D    100    90     20   10    100  70   100  90                         
11D    90     100    50   230   100  100  90   90                         
12D    100    100    95   80    100  100  90   90                         
13D    40     75     0    10    80   100  100  90                         
14D    50     0      0    0     100  80   70   90                         
15D    65     95     20   15    100  80   90   85                         
17D    100    100    60   30    100  100  90   35                         
18D    100    100    100  100   100  100  100  95                         
19D    100    100    0    50    100  100  100  95                         
20D    75     100    0    25    100  90   65   90                         
21D    100    100    100  80    100  100  90   95                         
22D    100    100    100  80    100  100  95   95                         
23D    100    100    98   95    100  100  100  95                         
25D    100    100    80   100   100  100  80   --                         
26D    100    100    75   100   100  100  80   --                         
27D    90     100    50   100   100  100  100  90                         
28D    75     50     50   0     100  100  90   65                         
30D    100    100    85   100   100  100  95   90                         
31D    85     75     0    25    100  25   0    35                         
32D    83     85     35   20    95   100  75   50                         
36D    100    100    50   100   100  100  100  75                         
37D    20     75     0    20    100  95   100  75                         
38D    85     95     40   60    100  100  75   85                         
39D    85     95     45   75    100  95   70   90                         
51D    60     60     35   0     25   0    0    30                         
52D    75     75     0    50    90   75   40    0                         
65D    100    100    80   100   100  100  --   80                         
______________________________________                                    
 A blank (--) indicates that the weed was not tested.                     

              TABLE II-E                                                  
______________________________________                                    
Pre-Emergence Herbicidal Activity                                         
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No.    FT     WG     WO   AMG   VL   MD   CD   YNS                        
______________________________________                                    
1E     0      0      0    0     0    0    0    20                         
2E     25     30     30   0     70   0    40   30                         
3E     25     20     0    0     0    0    0     0                         
4E     100    100    90   60    100  100  100  90                         
5E     50     60     40   50    50   60   90   50                         
6E     100    95     50   40    40   60   99   70                         
16E    80     100    50   60    100  90   90   90                         
20E    100    100    30   15    100  100  90   85                         
21E    100    100    --   30    100  95   100  80                         
______________________________________                                    
 A blank (--) indicates that the weed was not tested.                     

              TABLE II-F                                                  
______________________________________                                    
Pre-Emergence Herbicidal Activity                                         
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No.    FT     WG     WO   AMG   VL   MD   CD   YNS                        
______________________________________                                    
 1F    40     20     0    0     0    0    0    100                        
 2F    60     70     0    0     0    0    90   100                        
 3F    100    100    50   50    100  100  85   90                         
 4F    100    100    90   30    100  85   95   95                         
 5F    100    100    80   10    100  100  100  95                         
 6F    20     35     25   15    90   85   40   85                         
 7F    100    100    90   100   100  100  100  95                         
 8F    100    100    90   100   100  100  100  95                         
 9F    100    100    0    0     100  80   100  90                         
10F    100    100    100  100   100  100  100  95                         
11F    100    100    70   100   100  100  97   95                         
12F    100    100    60   100   100  100  100  95                         
13F    100    100    60   100   100  100  100  95                         
14F    80     100    50   80    100  100  90   90                         
15F    100    100    80   100   100  100  100  --                         
16F    50     75     0    25    100  100  95   60                         
17F    100    100    40   100   100  100  100  85                         
18F    100    100    0    20    100  100  80   70                         
20F    70     75     0    25    100  95   100  60                         
21F    50     60     0    0     100  80   80   60                         
22F    100    95     35   25    100  100  90   50                         
23F    95     100    40   20    100  100  90   50                         
24F    100    100    90   0     45   85   80   90                         
25F    100    100    25   60    100  100  100  75                         
34F    35     40     10   0     60   25   0    70                         
37F    50     60     0    0     60   0    50    0                         
38F    35     40     0    0     0    0    0     0                         
52F    85     100    30   95    100  100  --   80                         
53F    100    100    0    85    100  100  --   80                         
54F    100    100    90   25    100  100  --   80                         
______________________________________                                    
 A blank (--) indicates that the weed was not tested.                     

              TABLE II-G                                                  
______________________________________                                    
Pre-Emergence Herbicidal Activity                                         
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No.    FT      WG     WO   AMG    VL   MD    YNS                          
______________________________________                                    
 1G    100     100    90   100    100  100   80                           
 2G    100     100    90   100    100  100   80                           
 3G    100     100    90   100    100  100   80                           
 4G    100     100    90   100    100  100   80                           
 5G    100     100    90   100    100  100   80                           
 6G*   100     100    100  100    100  --    20                           
 7G    100     100    80   100    100  100   80                           
 8G     85     100    80   100    100  100   80                           
 9G    100     100    80   100    100  100   80                           
10G    100     100    80   100    100  100   80                           
11G    100     100    80   100    100  100   80                           
12G    100     100    80    90    100  100    0                           
13G    100     100    70   100    100  100    0                           
14G    100     100    75   100    100  100   90                           
15G    100     100    80   100    100  100   90                           
16G    100     100    90   100    100  100   80                           
17G    100     100    80   100    100  100   80                           
18G    100     100    90    85    100  100   80                           
19G    100     100    100  100    100  100   80                           
20G     70      95    10   100    100  100    0                           
21G    100     100    100  100    100  100   80                           
22G    100     100    90   100    100  100   80                           
23G    100     100    100  100    100  100   80                           
24G     0       80     0    25     80   70    0                           
25G    100     100    80   100    100  100   80                           
26G    100     100    100   80    100  100   80                           
27G    100     100    100  100    100  100   80                           
28G    100     100    90   100    100  100   80                           
______________________________________                                    
 A blank (--) indicates that the weed was not tested.                     
 *= Tested at 0.56 kg/ha.
Post-Emergence Herbicide Test:
This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the eight different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.
The results of the post-emergence herbicide test are reported in Table III.
                                  TABLE III-A                             
__________________________________________________________________________
Post-Emergence Herbicidal Activity                                        
Applicaton Rate - 4.48 kg/ha                                              
Cmpd.                                                                     
No. FT  WG WO  AMG VL  MD PW  CD YNS                                      
__________________________________________________________________________
 1A 60  70 20  40  60  60 35     60                                       
 2A 30  70  0  50  90  85 30     80                                       
 3A  0  30  0  70  100 90 55     70                                       
 4A 95  98 20  98  100 100                                                
                          30     95                                       
 5A 80  80 75  50  60  80  0     95                                       
 6A 40  40 10  60  100 100                                                
                          75     65                                       
 7A 60  75 40  60  100 75 100    75                                       
 8A 85  80 75  70  95  80 90     90                                       
 9A 85  80 75  70  95  80 90     90                                       
10A 95  85 90  60  95  95 80     95                                       
11A 50  80 35  55  100 100                                                
                          95     80                                       
12A 45  75 50  55  75  60 50     80                                       
13A 30  60 20  60  80  50 60     70                                       
14A 20  10 20  50  45  40 40      0                                       
15A 65  95  0  65  95  30 100    80                                       
16A 65  80 20  85  85  30 30     80                                       
17A 75  80 30  70  100 100                                                
                          85     90                                       
18A 100 95 10  100 100 100                                                
                          100    90                                       
19A 60  80 40  70  100 75 80     90                                       
20A 65  80 10  85  95  95 100    70                                       
21A 30  55  0  80  100 80 65     80                                       
22A  0  30  0  20  45   0 30     20                                       
23A 85  90 40  85  100 95 100    90                                       
24A  0  80  0  70  90  74 --     100                                      
25A 100 100                                                               
           75  90  100 100                                                
                          --     100                                      
26A 45  30  0  40  70  65      0 45                                       
27A 75  80 30  65  50  45     85 85                                       
28A 75  60 60  75  100 70     80 25                                       
29A 85  85 85  75  85  65     65 85                                       
30A 75  50 20  10   0   0     20 40                                       
31A 60  60 20  40  40  70     100                                         
                                 40                                       
32A 60  25 20  40  90  65     20 40                                       
33A 10   0  0  10  10  10     100                                         
                                 40                                       
34A 10  10  0   5  50  30     80  0                                       
35A  0   0  0  10  60  30     40  0                                       
36A  0   0  0  20  20  20      0  0                                       
37A  0   0  0  30  40  20     80  0                                       
38A 10  10 10  20  10  20     20 10                                       
39A 40  40 20   0   0   0      5 80                                       
40A 90  70 40  20  60  80     20 65                                       
41A 60  85 85  20  40  60     100                                         
                                 100                                      
42A 60  50 40  70  20  40     60 60                                       
43A 100 80 30  60  100 100    80 100                                      
44A 80  85  0  60  90  90     100                                         
                                 80                                       
45A 90  90 10  100 100 100    100                                         
                                 90                                       
46A 80  100                                                               
            0  60  100 100    100                                         
                                 100                                      
47A 100 100                                                               
            0  60  100 100    100                                         
                                 100                                      
48A 40  40 20  10  10  10     90 40                                       
49A 40  40 40  80  100 100    60 60                                       
50A 80  60 60  50  50  60     80 70                                       
51A 80  80 80  95  100 100    100                                         
                                 90                                       
52A 60  60 20  20  40  40     90 60                                       
53A 10  20 20   0   0   0      0 20                                       
54A 20  40 20   5   0   0      0 40                                       
55A 40  40 40  60  60  60     80 90                                       
56A 100 100                                                               
           75  80  100 100    100                                         
                                 90                                       
57A 80  80 80  95  100 100    100                                         
                                 90                                       
58A 60  70 10  70  10  10     20 80                                       
59A 100 100                                                               
           90  100 --  100    100                                         
                                 50                                       
60A 100 100                                                               
           100 100 --  100    100                                         
                                 70                                       
61A 90  85 90  85  --  100    100                                         
                                 80                                       
62A 100 85 100 75  100 100    100                                         
                                 35                                       
63A 70  80 20  100 100 100    35 40                                       
64A 75  75 90  70  90  70     40 40                                       
65A 100 70 100 55  90  95     100                                         
                                 40                                       
66A 100 75 100 90  95  95     100                                         
                                 20                                       
73A 100 100                                                               
           95  100 100 100    55 30                                       
74A 100 95 75  100 100 100    85 40                                       
75A 100 100                                                               
           30  95  80  100    80 40                                       
76A 80  80 75  75  100 95     95 25                                       
77A 80  80 80  90  90  80     90 80                                       
78A 80  85 75  85  80  95     100                                         
                                 50                                       
79A 50  65 35  90  100 100    90 --                                       
80A 40  40 10  20  60   0      0 30                                       
81A 90  70 60  40  60  60     90 70                                       
84A 100 100                                                               
           100 20  40  40     80 60                                       
88A 100 95 90  100 85  100    100                                         
                                 50                                       
89A 100 100                                                               
           75  85  75  85     95 50                                       
90A 100 85 90  90  85  90     100                                         
                                 55                                       
91A 100 100                                                               
           100 100 95  100    95 60                                       
105A                                                                      
    35  50 --  35  100 80     60 30                                       
117A                                                                      
    40  60  0  25  50  50     80 --                                       
118A                                                                      
    95  85 85  100 100 90     80 80                                       
121A                                                                      
    65  85 40  100 100 100    60 50                                       
125A                                                                      
    90  95 75  70  100 90     100                                         
                                 60                                       
126A                                                                      
    40  50 20  40  60  50     100                                         
                                 80                                       
127A                                                                      
    100 95 100 95  100 100       80                                       
128A                                                                      
    85  95 80  60  100 95        80                                       
129A                                                                      
    65  90 60  60  100 98        70                                       
130A                                                                      
    100 95 95  95  100 100       70                                       
131A                                                                      
     0  20  0   0  30  75     10  0                                       
132A                                                                      
    95  100                                                               
           100 80  95  95        50                                       
133A                                                                      
    80  95 90  60  85  85        60                                       
135A                                                                      
    70  100                                                               
           100 75  100 95        70                                       
__________________________________________________________________________

              TABLE III-B                                                 
______________________________________                                    
Post-Emergence Herbicidal Activity                                        
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No.    FT     WG     WO   AMG   VL   MD   CD   YNS                        
______________________________________                                    
 1B    85     95     20   95    100  100  95   95                         
 2B    90     90     80   100   90   90   --   80                         
 4B    60     60     90   40    60   60   90   70                         
 5B    40     60     10   20    40   40   90   80                         
 6B    40     50     10   60    20   20   60   50                         
 7B    80     80     80   60    60   90   6    60                         
 8B    100    80     60   30    80   80   80   80                         
 9B    70     70     60   40    60   60   80   70                         
10B    40     40     60   30    60   60   90   60                         
11B    80     90     60   45    90   90   100  80                         
12B    25     45     10   20    20   20   60   45                         
13B    100    100    95   70    60   60   80   60                         
15B    100    60     50   80    90   90   40   60                         
16B    60     60     80   80    90   90   60   65                         
17B    100    70     90   100   --   90   98   70                         
18B    100    85     100  85    --   100  100  65                         
19B    100    80     85   100   100  90   100  70                         
20B    90     65     90   85    70   60   100  40                         
21B    40     40     10   0     0    0    0     0                         
22B    40     70     80   90    90   100  95   40                         
25B    40     70     40   40    40   60   70   50                         
26B    65     70     80   40    90   80   70   80                         
27B    100    80     60   20    90   90   80   45                         
28B    90     60     60   60    60   60   40   70                         
29B    90     70     70   40    70   70   60   60                         
30B    100    90     70   50    100  100  80   80                         
31B    40     50     20   10    20   20   0    40                         
32B    25     40     40   90    100  100  40   40                         
33B    20     40     10   60    90   90   60   40                         
34B    90     80     80   80    100  100  80   50                         
35B    60     50     50   20    60   60   80   60                         
36B    100    80     80   75    --   100  100  45                         
37B    100    60     50   80    90   90   40   60                         
39B    90     80     25   30    30   45   50   30                         
40B    20     40     10   60    90   90   60   40                         
41B    25     45     10   20    20   20   60   45                         
42B    90     80     80   80    100  100  100  70                         
43B    80     90     95   97    100  100  100  50                         
44B    100    95     95   95    40   100  100  30                         
45B    30     65     0    30    45   40   65   50                         
46B    70     75     0    65    100  100  50   70                         
47B    100    100    100  90    100  100  100  85                         
48B    100    65     80   50    100  100  60   60                         
49B    60     70     70   40    80   70   30   50                         
50B    0      60     40   60    100  90   20   30                         
51B    100    75     80   40    100  50   20   30                         
52B    90     100    100  100   100  100  100  40                         
53B    60     70     70   70    90   65   40   60                         
54B    100    100    85   100   100  100  100  60                         
55B    95     85     90   100   100  100  90   45                         
56B    85     100    0    10    15   95   40   50                         
57B    85     70     65   0     0    0    0    35                         
58B    20     40     10   15    70   40   35   40                         
59B    100    95     100  95    100  95   100  40                         
60B    65     75     75   80    90   85   80   60                         
61B    80     80     70   95    80   85   80   50                         
62B    100    80     25   80    75   80   85   35                         
63B    100    100    40   95    95   100  95   50                         
64B    75     70     50   90    90   100  90   50                         
65B    100    80     80   60    85   60   0    --                         
66B    98     90     60   35    --   100  60   90                         
67B    70     65     20   15    95   40   70   45                         
71B    95     50     50   80    80   80   65   50                         
72B    100    85     75   75    65   85   70   60                         
73B    100    95     95   85    75   85   95   40                         
74B    100    85     95   90    80   95   65   50                         
75B    100    80     80   30    50   60   100  40                         
81B    50     80     35   70    70   90   80   10                         
82B    25     60     50   35    50   90   50   25                         
91B    80     60     40   60    75   90   60   75                         
101B   10     35     --   30    75   70   40   50                         
______________________________________                                    
 (--) = Specie did not germinate for some reason.                         

              TABLE III-C                                                 
______________________________________                                    
Post-Emergence Herbicidal Activity                                        
Application Rate -- 4.48 kg/ha                                            
Cmpd.                                                                     
No.    FT     WG     WO   AMG   VL   MD   CD   YNS                        
______________________________________                                    
1C     98     95     70   60    100  55   100  90                         
______________________________________                                    

              TABLE III-D                                                 
______________________________________                                    
Post-Emergence Herbicidal Activity                                        
Application Rate - 4.48 kg/ha                                             
Cmpd.                                                                     
No.   FT     WG     WO   AMG   VL   MD    CD   YNS                        
______________________________________                                    
 1D   95     75     85   70    100  90    85   40                         
 2D   45     70     95   75    100  90    100  65                         
 3D   100    80     100  90    --   100   100  80                         
 4D   100    80     100  100   --   100   85   75                         
 5D   90     70     45   60     95  70    60   80                         
 6D   95     75     80   70    100  90    90   65                         
 9D   100    90     90   100   100  100   95   85                         
10D   45     75     10   15    100  100   20   75                         
11D   100    70     60   75    100  100   100  45                         
12D   100    75     100  100   100  100   90   90                         
13D   30     55      0   30     60  60    15   60                         
14D   20     65      0   40     70  60    40   25                         
15D   20     75     30   20    100  70    60   40                         
17D   85     80     50   65     95  95    100  60                         
18D   100    95     100  100   100  100   100  75                         
19D   20     95     30   100   100  35    30   70                         
20D   30     80     15   100   100  45    20   70                         
21D   100    80     100  55    100  90    100  80                         
22D   100    80     100  60    100  95    95   95                         
23D   100    90     90   100   100  100   85   70                         
25D   70     75     50   85     90  85    60   75                         
26D   100    85     85   95     95  95    90   60                         
27D   90     90     60   100   100  100   100  --                         
28D   15     45     20   50     75  80    15   30                         
30D   100    100    80   85     85  85    100  --                         
31D   80     90     100  100   100  100   100  60                         
32D   75     85     85   75     75  90    95   50                         
36D   35     50     35   70      50 50    35   60                         
37D   60     75     15   70     70  90    90   40                         
38D   95     90     65   70     90  90    100  50                         
39D   95     85     30   50     70  80    100  50                         
51D   60     75     60   35     30  60    40   60                         
52D   60     75     25   100   100  100   100  75                         
65D   70     50     70   90     80  85    --   80                         
______________________________________                                    
 A blank (--) indicates the weed was not tested.                          

              TABLE III-E                                                 
______________________________________                                    
Post-Emergence Herbicidal Activity                                        
Application Rate - 4.48 kg/ha                                             
Cmpd.                                                                     
No.   FT     WG     WO   AMG   VL   MD    CD   YNG                        
______________________________________                                    
1E    20     20     10   20    40   40    20   40                         
2E     0     60     60   50    70   30     0   15                         
3E    20     20      0   10     0   20     0   20                         
4E    85     90     100  45    75   30    80   65                         
5E    55     50     60   50    75   85    65   --                         
6E    70     70     50   60    80   70    90   --                         
16E   95     95     40   100   100  100   100  90                         
20E   95     75     35   40    95   75    35   80                         
21E   80     70     30   45    80   90    50   70                         
______________________________________                                    
 A blank (--) indicates the weed was not tested.                          

              TABLE III-F                                                 
______________________________________                                    
Post-Emergence Herbicidal Activity                                        
Application Rate - 4.48 kg/ha                                             
Cmpd.                                                                     
No.   FT     WG     WO   AMG   VL   MD    CD   YNG                        
______________________________________                                    
 1F   60     40     20   30    40   40    50   60                         
 2F   50     40     10   20    20   20    40   60                         
 3F   100    100    85   100   100  100   100  75                         
 4F   100    100    95   85    100  95    100  60                         
 5F   95     95     100  65    90   25    70   45                         
 6F   40     30      0   20    90   25    20   70                         
 7F   100    100    100  100   100  100   100  90                         
 8F   100    95     100  100   100  100   100  70                         
 9F   65     65      0   20    80   65    90   80                         
10F   100    100    100  100   100  100   100  70                         
11F   85     90     90   85    90   80    30   60                         
12F   100    90     65   80    100  100   100  50                         
13F   100    95     100  100   100  100   90   --                         
14F   100    100    100  100   100  100   100  50                         
15F   25     35     15   30    80   25    20    0                         
16F   100    85     70   75    90   90    50   --                         
17F   100    100    100  100   100  100   100  --                         
18F   90     85     85   85    90   95    70   40                         
20F   40     60     10   60    100  100   100  50                         
21F   35     60     10   60    100  100   80   60                         
22F   95     95     35   100   100  100   90   50                         
23F   100    100    40   100   100  100   90   50                         
24F   100    75     100  60    --   100   100  60                         
25F   95     95     90   95    100  100   95   35                         
34F   50     40      0   35    50   70    30   50                         
37F   20     60       0  30    30   50    50   50                         
38F   25     50      0   25    25   50    20   20                         
52F    0     60     50   50    10   50    --   20                         
53F    0     50      0   50    50   50    --   30                         
54F   90     75     60   50    50   80    --   80                         
______________________________________                                    
 A blank (--) indicates the weed was not tested.                          

              TABLE III-G                                                 
______________________________________                                    
Post-Emergence Herbicidal Activity                                        
Application Rate - 4.48 kg/ha                                             
Cmpd.                                                                     
No.   FT     WG      WO    AMG   VL    MD    YNG                          
______________________________________                                    
 1G   100    95      90    90    100   100   80                           
 2G   100    100     100   100   100   100   80                           
 3G   100    100     95    100   100   100   90                           
 4G   100    100     100   100   100   100   90                           
 5G   100    100     100   100   100   100   100                          
 6G*  10     80      50    75    40    --     0                           
 7G   70     75      70    90    90    80    80                           
 8G   50     80      70    90    90    80    30                           
 9G   70     80      70    90    90    80    30                           
10G   75     80      70    80    60    50    70                           
11G   70     80      70    80    80    80    80                           
12G   100    75      90    75    80    80    80                           
13G   60     70      70    100   100   100   80                           
14G   20     70      40    60    80    80    70                           
15G   90     70      70    75    80    90    70                           
16G   50     70      80    60    80    90    70                           
17G   90     60      70    65    80    80    80                           
18G   30     50      80    95    95    80    70                           
19G   100    100     95    90    100   100   80                           
20G   10     40       5    70    80    90    70                           
21G   95     90      95    95    100   100   70                           
22G   80     90      90    80    100   100   70                           
23G   90     80      80    80    90    80    30                           
24G    0     30       0    40    80    20     0                           
25G    0     20       0    10    10    20     0                           
26G   80     70      70    80    80    80    70                           
27G   90     90      90    80    80    90    60                           
28G   70     65      50    80    80    80    70                           
______________________________________                                    
 A blank (--) indicates the weed was not tested.                          
 * Tested at 0.56 kg/ha.
Pre-Emergence Multi-Weed Herbicide Test
Several compounds were evaluated at an application rate of 2 lb/acre (2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for pre-emergence activity against a larger number of weed species.
The process was generally similar to the pre-emergence herbicide test described above except that only 300 or 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.
Redroot pigweed (PW) and curly doct (CD) were eliminated in this test and the following weed species were added:
______________________________________                                    
Grasses:                                                                  
______________________________________                                    
downy brome  Bromus tectorum                                              
                           (DB)                                           
annual ryegrass                                                           
             Lolium multiflorum                                           
                           (ARG)                                          
rox-orange   Sorghu bicolor                                               
                           (SHC)                                          
sorghum                                                                   
hemp sesbania                                                             
             Sesbania exaltata                                            
                           (SESB)                                         
nightshade   Solanum sp.   (SP)                                           
cocklebur    Xattiium sp.  (CB)                                           
______________________________________
The results of the 2.24 kg/ha test are shown in Table IV and the results of the 1.12 kg/ha test are shown in Table VI.
Post-Emergence Multi-Weed Herbicide Test
Several compounds were evalated at an application rate of 2 lb/acre (2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for post-emergence activity against the larger number of weed species that are used in the pre-emergent multi-herbicide test.
The process was generally similar to the post-emergence herbicide test described above except that only 300 or 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.
The results of the 2.24 kg/ha test are shown in Table V and the results for the 1.12 kg/ha test are shown in Table VII.
                                  TABLE IV-A                              
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 2.24 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP                                   
                                       MD YNS                             
                                             CB                           
__________________________________________________________________________
67A 20 90 25   98                                                         
                  80                                                      
                    60 90 45  90   45                                     
                                     20                                   
                                        85                                
                                          85 15                           
68A 65 98 98  100                                                         
                 100                                                      
                    60 95 100 100 100                                     
                                     80                                   
                                       100                                
                                          95 100                          
69A 65 100                                                                
          70  100                                                         
                 100                                                      
                    65 95 100 95   70                                     
                                     65                                   
                                       100                                
                                          90 --                           
70A 98 100                                                                
          100 100                                                         
                 100                                                      
                    90 98 90  100  90                                     
                                     60                                   
                                       100                                
                                          95 80                           
71A 60 20 100 100                                                         
                 100                                                      
                    80 95 35  40  100                                     
                                     20                                   
                                        90                                
                                          100                             
                                             40                           
72A 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 90  100                                     
                                     60                                   
                                       100                                
                                          100                             
                                             20                           
83A 15 45 25   90                                                         
                  15                                                      
                      5                                                   
                       90 45  35   20                                     
                                      0                                   
                                        20                                
                                          75 --                           
86A 20  0 15   60                                                         
                  60                                                      
                    20 70 25  45  100                                     
                                     20                                   
                                       100                                
                                          15 35                           
87A 100                                                                   
       90 85  100                                                         
                  85                                                      
                    25 30 35  85  100                                     
                                     85                                   
                                       100                                
                                          95 40                           
__________________________________________________________________________

                                  TABLE VI-A                              
__________________________________________________________________________
Post-Emergence Multi-weed Herbicide Test                                  
Application Rate - 2.24 hg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
86A 60 100                                                                
          50   90                                                         
                 50 60 90 70  100 100                                     
                                      20                                  
                                        100                               
                                           20 --                          
87A 95 100                                                                
          30  100                                                         
                 80 70 80 95  100 100                                     
                                     100                                  
                                        100                               
                                           70 --                          
__________________________________________________________________________

                                  TABLE V-A                               
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
 82A                                                                      
    35 100                                                                
          85  100                                                         
                  65                                                      
                    60 90 50  90   60                                     
                                     30  97                               
                                           90 40                          
 85A                                                                      
    100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    85 100                                                
                          20  10  100                                     
                                     65 100                               
                                           100                            
                                              30                          
 92A                                                                      
    15  20                                                                
          45  100                                                         
                  90                                                      
                    40 80 95  95  100                                     
                                     25 100                               
                                           90 40                          
 93A                                                                      
    30  75                                                                
          40  100                                                         
                 100                                                      
                    60 90 100 100 100                                     
                                     35 100                               
                                           90 40                          
 94A                                                                      
    30  70                                                                
          40  100                                                         
                 100                                                      
                    30 65 95  85  100                                     
                                      0 100                               
                                           90 30                          
 95A                                                                      
     0  0  0   85                                                         
                  60                                                      
                    15 70 65  60  100                                     
                                     80  90                               
                                           10 20                          
 96A                                                                      
    95 100                                                                
          98  100                                                         
                 100                                                      
                    70 100                                                
                          100 95   90                                     
                                     80 100                               
                                           95 --                          
 97A                                                                      
    100                                                                   
       100                                                                
          98  100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 95  100                                     
                                     70 100                               
                                           95 100                         
 98A                                                                      
    10  0  0   0  20                                                      
                    25 70  0  20   0  0  80                               
                                           30 --                          
 99A                                                                      
    15  0  0   75                                                         
                  25                                                      
                     0 20 30  60   15                                     
                                     20  30                               
                                           25  0                          
100A                                                                      
     0  0  0   0  0  0 20 10   0   0  0  15                               
                                            0 --                          
101A                                                                      
    100                                                                   
        98                                                                
          95  100                                                         
                 100                                                      
                    70 98 100 100 100                                     
                                     20 100                               
                                           95 --                          
102A                                                                      
    25  20                                                                
          35  100                                                         
                 100                                                      
                    45 95 70  100 100                                     
                                     60 100                               
                                           90 --                          
103A                                                                      
    80  60                                                                
          45  100                                                         
                 100                                                      
                    40 90 65  90  100                                     
                                      0 100                               
                                           95  0                          
106A                                                                      
    100                                                                   
       100                                                                
          60   40                                                         
                  95                                                      
                    35 100                                                
                          35  90  100                                     
                                     70 100                               
                                           90 --                          
107A                                                                      
    100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    90 100                                                
                          100 100 100                                     
                                     80 100                               
                                           95 30                          
108A                                                                      
    100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    85 100                                                
                          100 100 100                                     
                                     30 100                               
                                           95 100                         
109A.sup.a                                                                
    65  20                                                                
          85  100                                                         
                  98                                                      
                    60 90 30  50  100                                     
                                     50 100                               
                                           90 100                         
110A                                                                      
     0  60                                                                
          30  100                                                         
                  65                                                      
                    25 65 25  30  100                                     
                                      0 100                               
                                           60  0                          
111A                                                                      
    100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    75 98 100 100 100                                     
                                     90 100                               
                                           -- 70                          
112A                                                                      
    100                                                                   
       100                                                                
          90  100                                                         
                 100                                                      
                    95 100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           -- --                          
113A                                                                      
    65  95                                                                
          40  100                                                         
                 100                                                      
                    30 90 70  100 100                                     
                                      0 100                               
                                           -- 30                          
114A                                                                      
    70 100                                                                
          25  100                                                         
                 100                                                      
                    40 100                                                
                          100 100 100                                     
                                     30 100                               
                                           95 80                          
115A                                                                      
    100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     45 100                               
                                           85 100                         
116A                                                                      
    25  15                                                                
          20  100                                                         
                  65                                                      
                    35 65 45  50  100                                     
                                      0 100                               
                                           95 10                          
119A                                                                      
    100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     95 100                               
                                           95 90                          
120A                                                                      
    100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    95 100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           90 100                         
122A                                                                      
    80  80                                                                
          45  100                                                         
                  60                                                      
                    65 70 100 100 100                                     
                                     100                                  
                                        100                               
                                           90 100                         
123A                                                                      
     0 100                                                                
          50  100                                                         
                  85                                                      
                     0 60 100 90  100                                     
                                     80 100                               
                                           100                            
                                              20                          
124A                                                                      
    25  50                                                                
          65   90                                                         
                  65                                                      
                     0 40 75  80  100                                     
                                     40  90                               
                                           80 60                          
__________________________________________________________________________
 .sup.a application rate was 0.56 kg/ha.                                  

                                  TABLE VII-A                             
__________________________________________________________________________
Post-Emergence Multi-weed Herbicide Test                                  
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
 82A                                                                      
    60 40 10  98 35 10 30  70 100 100                                     
                                     100                                  
                                         90                               
                                           45 --                          
 85A                                                                      
    60 60 35  100                                                         
                 45 60 85  50 100 100                                     
                                     100                                  
                                        100                               
                                           60 --                          
 92A                                                                      
    70 55 20  80 80 45 100                                                
                           95  90  80                                     
                                     20  95                               
                                           70 90                          
 93A                                                                      
    90 90 70  95 95 75 90  98  95  85                                     
                                     35 100                               
                                           60 90                          
 94A                                                                      
    100                                                                   
       85 45  90 100                                                      
                    90 100                                                
                          100  90  90                                     
                                     30 100                               
                                           60 85                          
 95A                                                                      
    20 60  0  80 70  0 45  60  75  90                                     
                                      0  65                               
                                           20 --                          
 96A                                                                      
    95 100                                                                
          90  95 100                                                      
                    80 95 100 100 100                                     
                                     70 100                               
                                           70 90                          
 97A                                                                      
    100                                                                   
       100                                                                
          95  100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     90 100                               
                                           70 100                         
 98A                                                                      
    20  0  0  45 10 50 30  20  65 100                                     
                                      0  75                               
                                           35 80                          
 99A                                                                      
    25 75 15  80 65 10 25  85 100 100                                     
                                     80 100                               
                                           10 --                          
100A                                                                      
    10 35  0  70 50  5 20  30  70  40                                     
                                      0 100                               
                                           10 100                         
101A                                                                      
    30 60 25  100                                                         
                 60 60 80 100 100 100                                     
                                     30 100                               
                                           70 --                          
103A                                                                      
    90 100                                                                
          25  100                                                         
                 100                                                      
                    80 100                                                
                          100 100 100                                     
                                     15 100                               
                                           40 --                          
104A                                                                      
    98 98 25  98 100                                                      
                    15 100                                                
                          100 100 100                                     
                                     60 100                               
                                           95 --                          
106A                                                                      
    75 90 30  90 70 25 100                                                
                          100 100 100                                     
                                     80 100                               
                                           75 --                          
107A                                                                      
    100                                                                   
       100                                                                
          80  90 85 100                                                   
                       100                                                
                          100 100 100                                     
                                     60 100                               
                                           40 --                          
108A                                                                      
    100                                                                   
       100                                                                
          65  90 60 95 100                                                
                          100 100 100                                     
                                     90 100                               
                                           90 --                          
109A.sup.a                                                                
    90 60 45  90 70 60 98  95  95 100                                     
                                     98  80                               
                                           55 --                          
110A                                                                      
    50 50 20  100                                                         
                 50 10 40 100  98  98                                     
                                     20 100                               
                                           35 45                          
111A                                                                      
    85 90 80  90 70 60 95 100  90 100                                     
                                     65 100                               
                                           80 60                          
112A                                                                      
    100                                                                   
       100                                                                
          90  100                                                         
                 100                                                      
                    95 100                                                
                          100 100 100                                     
                                     45 100                               
                                           95 70                          
113A                                                                      
    70 50 20  90 60 50 80  95  95 100                                     
                                     60 100                               
                                           -- 60                          
114A                                                                      
    85 100                                                                
          15  100                                                         
                 100                                                      
                    60 00 100 100 100                                     
                                     100                                  
                                        100                               
                                           60 --                          
115A                                                                      
    100                                                                   
       100                                                                
          45  100                                                         
                 100                                                      
                    80 100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           90 --                          
116A                                                                      
    80 60 25  90 35 40 45  75  90 100                                     
                                     40  90                               
                                           75 60                          
119A                                                                      
    60 70 30  95 70 20 90 100 100 100                                     
                                     90 100                               
                                           30 85                          
120A                                                                      
    75 90 60  95 80 45 100                                                
                          100  90 100                                     
                                     65 100                               
                                           35 100                         
122A                                                                      
    60 90 15  100                                                         
                 30 15 15 100 100 100                                     
                                     75 100                               
                                           45 95                          
123A                                                                      
     0 100                                                                
          35  100                                                         
                 50 15 85 100 100 100                                     
                                     100                                  
                                        100                               
                                           70 85                          
124A                                                                      
    25 100                                                                
          35  40 35  0 40  95 100 100                                     
                                     100                                  
                                        100                               
                                           85 75                          
__________________________________________________________________________
 .sup.a Application rate was 0.56 kg/ha.                                  
 A dash mark (--) is used in Tables II-VII to indicate that no percent    
 control number was available.                                            

                                  TABLE IV-B                              
__________________________________________________________________________
Pre-Emergence Multi-Weed Herbicide Test                                   
Application Rate - 2.24 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP                                   
                                       MD YNS                             
                                             CB                           
__________________________________________________________________________
14B 80 100                                                                
          100 100                                                         
                 100                                                      
                    80 95  70  60 100                                     
                                     40                                   
                                        85                                
                                          100                             
                                             10                           
21B 85 100                                                                
          90  100                                                         
                 100                                                      
                    85 100                                                
                          100 100 100                                     
                                     70                                   
                                       100                                
                                          95 100                          
24B 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     75                                   
                                       100                                
                                          95 --                           
38B 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                           20  10 100                                     
                                     20                                   
                                        95                                
                                          100                             
                                             20                           
88B 75 100                                                                
          60  100                                                         
                 100                                                      
                    70 60  20  40 100                                     
                                      0                                   
                                       100                                
                                          60 20                           
89B 20  60                                                                
          30   85                                                         
                  95                                                      
                    55 40  15  20  65                                     
                                      0                                   
                                       100                                
                                          35 50                           
90B 60 100                                                                
          60  100                                                         
                 100                                                      
                    45 30 100 100 100                                     
                                     15                                   
                                       100                                
                                          50 85                           
103B                                                                      
    95 100                                                                
          75  100                                                         
                 100                                                      
                    50 85 100 100 100                                     
                                     80                                   
                                       100                                
                                          80 40                           
104B                                                                      
    60 100                                                                
          60  100                                                         
                 100                                                      
                    45 30 100 100 100                                     
                                     15                                   
                                       100                                
                                          50 85                           
__________________________________________________________________________
 (--) = Specie did not germinate for some reason.                         

                                  TABLE V-B                               
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicde Test                                   
Application Rate - 2.24 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP                                   
                                       MD YNS                             
                                             CB                           
__________________________________________________________________________
24B 35  25                                                                
          45   60                                                         
                 65 85 90 100 100 -- 90                                   
                                       100                                
                                          65 --                           
88B 60  30                                                                
          30   90                                                         
                 100                                                      
                    80 100                                                
                          100 100 100                                     
                                     30                                   
                                       100                                
                                          20 100                          
89B 50  70                                                                
          35   90                                                         
                 60 35 20 100  90 100                                     
                                     35                                   
                                       100                                
                                          15 100                          
90B 30 100                                                                
          40  100                                                         
                 70 10 25 100 100 100                                     
                                     30                                   
                                        90                                
                                          50  95                          
103B                                                                      
    95 100                                                                
          70  100                                                         
                 65 75 65 100 100 100                                     
                                     65                                   
                                       100                                
                                          50 100                          
104B                                                                      
    30 100                                                                
          40  100                                                         
                 70 10 25 100 100 100                                     
                                     30                                   
                                        90                                
                                          50  95                          
__________________________________________________________________________
 (--) = Specie dd not germinate for some reason.                          

                                  TABLE VI-B                              
__________________________________________________________________________
Pre-Emergence Multi-Weed Herbicide Test                                   
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No.  DB FT ARG WG SHC WO BSG                                              
                            AMG SESB                                      
                                    VL SP MD YNS                          
                                                CB                        
__________________________________________________________________________
 1B  25  10                                                               
           30   85                                                        
                   55  0 --  55 --  100                                   
                                       --  75                             
                                             75 35                        
23B  55  95                                                               
           90  100                                                        
                   95*                                                    
                      95 95  98 80  -- 10 100                             
                                             95 --                        
68B  65 100                                                               
           60  100                                                        
                   100*                                                   
                       6 90 100 90  100                                   
                                       20 100                             
                                             30 40                        
69B  70 100                                                               
           60  100                                                        
                   100*                                                   
                      95 95 100 95  100                                   
                                        0 100                             
                                             85 25                        
70B  60 100                                                               
           75  100                                                        
                   100*                                                   
                      85 100                                              
                            100 90  100                                   
                                       25 100                             
                                             90 25                        
76B  100                                                                  
        100                                                               
           85  100                                                        
                  100*                                                    
                      85 98 100 95  -- 35 100                             
                                             95 --                        
78B  40  70                                                               
           15   95                                                        
                   75*                                                    
                      25 80  65 75  --  0 100                             
                                             80 --                        
79B  100                                                                  
        100                                                               
           100 100                                                        
                  100 98 100                                              
                            100 85  100                                   
                                       85 100                             
                                             95 --                        
80B  98 100                                                               
           95  100                                                        
                  100 60 98  99 90  100                                   
                                       35 100                             
                                             85 --                        
83B  20 100                                                               
           60  100                                                        
                   100*                                                   
                      40 90  85 65  100                                   
                                        0 100                             
                                             85 --                        
84B   0  90                                                               
           25   98                                                        
                   100*                                                   
                      30 90  20 35  100                                   
                                        5 100                             
                                             50 --                        
85B  80 100                                                               
           50  100                                                        
                  100 60 90 100 90  100                                   
                                        0 100                             
                                             95 --                        
86B  60  90                                                               
           40  100                                                        
                  100 60 70  35 60  100                                   
                                       100                                
                                          100                             
                                             -- --                        
87B   0  90                                                               
           15  100                                                        
                   85 15 70  40 60  100                                   
                                       40  90                             
                                             20 --                        
92B  20  40                                                               
           10   95                                                        
                   40 10 60  65 30  100                                   
                                        0  55                             
                                             60  0                        
93B  60  95                                                               
           20  100                                                        
                  100 75 100                                              
                            100 100 100                                   
                                        0 100                             
                                             40 35                        
94B   0  80                                                               
           40  100                                                        
                   95 25 85  80 40  100                                   
                                       10  85                             
                                             55 10                        
95B  98 100                                                               
           30  100                                                        
                  100 40 90 100 100 100                                   
                                       40 100                             
                                             90 30                        
96B  100                                                                  
        100                                                               
           75  100                                                        
                  100 95 100                                              
                            100 100 100                                   
                                       60 100                             
                                             85 100                       
97B  100                                                                  
        100                                                               
           90  100                                                        
                  100 95 100                                              
                            100 100 100                                   
                                       60 100                             
                                             95 100                       
98B  95 100                                                               
           100 100                                                        
                  100 80 100                                              
                            100 100 100                                   
                                       50 100                             
                                             100                          
                                                60                        
 99B**                                                                    
     -- 100                                                               
           75  100                                                        
                   100*                                                   
                      20 75  50 75   95                                   
                                        0 -- 85 30                        
100B 100                                                                  
         98                                                               
           98  100                                                        
                  100 90 95 100 75  100                                   
                                       70 100                             
                                             95 40                        
102B  0 100                                                               
           25  100                                                        
                   90 75 95  60 60  100                                   
                                       30 100                             
                                             90 --                        
__________________________________________________________________________
 *seedling johnsongrass (Sroghum halepense) was substituted for roxorgange
 sorghum.                                                                 
 **Application rate was 0.56 kg/ha                                        
 (--) = Specie did not germinate for some reason.                         

                                  TABLE VII-B                             
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicide Test                                  
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No.  DB FT ARG WG SHC                                                     
                     WO BSG                                               
                           AMG SESB                                       
                                   VL SP MD YNS                           
                                               CB                         
__________________________________________________________________________
 1B  45 35 40  90 35 10 --  60 --   75                                    
                                      --  60                              
                                            50 55                         
23B  90 100                                                               
           80  90  90*                                                    
                     90 90  80  90  90                                    
                                      40  70                              
                                            25 --                         
68B  50 60 40  85  80*                                                    
                     75 100                                               
                            95  90  85                                    
                                      55 100                              
                                            40 --                         
69B  70 80 35  90  90*                                                    
                     80 90  80  85  90                                    
                                      20  90                              
                                            25 --                         
70B  100                                                                  
        90 80  100                                                        
                  100*                                                    
                     95 100                                               
                           100  95  80                                    
                                      30  75                              
                                            45 90                         
76B  100                                                                  
        100                                                               
           98  100                                                        
                  100* 100                                                
                     100                                                  
                        100                                               
                           100 100 60 100                                 
                                         40 --                            
78B  100                                                                  
        90 80  85 100*                                                    
                     70 90 100 100 100                                    
                                       0  90                              
                                            45 --                         
79B  80 35 45  70  60*                                                    
                     70 70  45  98 100                                    
                                      35  90                              
                                            20 --                         
80B  60 70 25  90  60*                                                    
                     60 85  70 90  100                                    
                                      15 100                              
                                            25 100                        
85B  95 100                                                               
           65  100                                                        
                  80 90 100                                               
                           100 100 100                                    
                                      25 100                              
                                            85 --                         
86B  30 60 20  75 50 50 60  50  65 100                                    
                                      10 100                              
                                            20 80                         
87B   0  0  0  100                                                        
                  45 20 30  60  90  80                                    
                                       0 100                              
                                            30 45                         
92B  20 80 10  85 15  0 30 100  40 100                                    
                                       0  60                              
                                            60 30                         
93B  70 100                                                               
           25  100                                                        
                  100                                                     
                     85 100                                               
                           100 100 100                                    
                                      100                                 
                                         100                              
                                            80 --                         
94B  20 70 30  90 80 30 20 100 100 100                                    
                                      60  30                              
                                            30 100                        
95B  60 90 15  95 95 25 90 100 100 100                                    
                                      75 100                              
                                            70 100                        
96B  50 80  0  90 70 30 100                                               
                           100 100 100                                    
                                      40 100                              
                                            20 100                        
97B  65 100                                                               
           35  100                                                        
                  75 70 80 100 100 100                                    
                                      50 100                              
                                            50 100                        
98B  95 100                                                               
           65  95 90 100                                                  
                        95 100 100  90                                    
                                      40  80                              
                                            60 95                         
 99B**                                                                    
     -- 100                                                               
           95  90  90*                                                    
                     90 100                                               
                            25  80  40                                    
                                      100                                 
                                         -- 35 75                         
100B 65 75 60  80 75 60 85 100 100 100                                    
                                      45 100                              
                                            65 60                         
102B 30 75 20  80 60  0 40  70 100 100                                    
                                      30 100                              
                                            75 --                         
__________________________________________________________________________
 *=Seedling johnsongram (Sorghum halepense) was substituted for roxorange 
 sorghum.                                                                 
 **=Application rate was 0.56 kg/ha.                                      
 (--)=Specie did not germinate for some reason.                           

                                  TABLE IV-C                              
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
2C  0  100                                                                
          0   100                                                         
                 -- 45 70 65  50  100                                     
                                     15 100                               
                                           90 --                          
__________________________________________________________________________
 (--) = Not tested.                                                       

                                  TABLE V-C                               
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity                             
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
2D  0  30 0   100                                                         
                 -- 0  60 85  95  100                                     
                                     100                                  
                                        90 40 --                          
__________________________________________________________________________
 (--) = Not tested.                                                       

                                  TABLE IV-D                              
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 2.24 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
 7D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           95 100                         
 8D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           95 --                          
16D.sup.a                                                                 
     70                                                                   
       100                                                                
           65 100                                                         
                 100                                                      
                    60 98  55 100 100                                     
                                      90                                  
                                        100                               
                                           90 --                          
24D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           100                            
                                              --                          
29D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                      30                                  
                                        100                               
                                           95  80                         
33D  75                                                                   
        15                                                                
           60  90                                                         
                  90                                                      
                    20 95 100 100 100                                     
                                      60                                  
                                        100                               
                                           95 100                         
53D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    90 100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           95 100                         
57D 100                                                                   
       100                                                                
           25 100                                                         
                 100                                                      
                    30 25 100 100 100                                     
                                     100                                  
                                        100                               
                                           95 100                         
64D.sup.a                                                                 
    --  0  0   95                                                         
                  35                                                      
                     0 15  50  75  75                                     
                                      25                                  
                                        -- 75  40                         
66D.sup.a                                                                 
    --  0  15  15                                                         
                  50                                                      
                    20 50 100 100  75                                     
                                      0 -- 90 100                         
67D.sup.a                                                                 
    --  0  0  100                                                         
                 100                                                      
                     0 25  95  75  50                                     
                                      25                                  
                                        -- 30  75                         
69D.sup.a                                                                 
    --  30                                                                
           0  100                                                         
                 100                                                      
                     0 70 100 100 100                                     
                                      35                                  
                                        -- 95 100                         
70D.sup.a                                                                 
    -- 100                                                                
           10 100                                                         
                 100                                                      
                    25 65 100 100 100                                     
                                      0 -- 95 100                         
__________________________________________________________________________
 (--) = Not tested.                                                       
 .sup.a = Tested at 0.28 kg/ha.                                           

                                  TABLE V-D                               
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
34D  90                                                                   
        85                                                                
          30   95                                                         
                 -- 45  98                                                
                           75 100 100                                     
                                     40 100                               
                                           50 --                          
35D 100                                                                   
        85                                                                
          70  100                                                         
                 -- 90 100                                                
                          100 100 100                                     
                                     40 100                               
                                           75 --                          
40D 100                                                                   
       100                                                                
          20  100                                                         
                 -- 70 100                                                
                           98  98 100                                     
                                     20 100                               
                                           50 --                          
41D 100                                                                   
       100                                                                
          80  100                                                         
                 -- 60 100                                                
                          100 100 100                                     
                                     25 100                               
                                           95 --                          
42D  50                                                                   
        60                                                                
          40   85                                                         
                 -- 30 100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           90 --                          
43D  90                                                                   
        95                                                                
          60  100                                                         
                 -- 30  98                                                
                          100  98 100                                     
                                     45 100                               
                                           95 --                          
44D  60                                                                   
       100                                                                
          20  100                                                         
                 -- 60 100                                                
                          100  90 100                                     
                                     20 100                               
                                           80 --                          
45D  95                                                                   
       100                                                                
          35  100                                                         
                 -- 60  90                                                
                          100 100 100                                     
                                      0 100                               
                                           90 --                          
46D 100                                                                   
       100                                                                
          90  100                                                         
                 -- 95 100                                                
                          100 100 100                                     
                                     40 100                               
                                           95 --                          
47D 100                                                                   
       100                                                                
          100 100                                                         
                 -- 98 100                                                
                          100  98 100                                     
                                     30 100                               
                                           95 --                          
48D 100                                                                   
       100                                                                
          100 100                                                         
                 -- 100                                                   
                       100                                                
                          100 100 100                                     
                                     90 100                               
                                           100                            
                                              --                          
49D 100                                                                   
       100                                                                
          100 100                                                         
                 -- 100                                                   
                       100                                                
                          100 100 100                                     
                                     90 100                               
                                           -- --                          
50D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    85 100                                                
                          100 100 100                                     
                                     90 100                               
                                           98 --                          
54D 100                                                                   
       100                                                                
          85  100                                                         
                 100                                                      
                    15 100                                                
                           25 100 100                                     
                                     65 100                               
                                           95 100                         
55D  85                                                                   
       100                                                                
          35  100                                                         
                  98                                                      
                    15 100                                                
                           15 100 100                                     
                                     65 100                               
                                           95 --                          
56D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           100                            
                                              100                         
58D  98                                                                   
       100                                                                
          40   95                                                         
                  40                                                      
                    20  95                                                
                          100 100 100                                     
                                     85 100                               
                                           100                            
                                              95                          
59D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    90 100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           85 80                          
60D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     75 100                               
                                           85 80                          
__________________________________________________________________________
 (--) = Not tested.                                                       

                                  TABLE VI-D                              
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 0.56 kg/ha                                             
Cmd.                                                                      
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
61D -- 100                                                                
          65  100                                                         
                 65 20  80                                                
                          20  40   80                                     
                                     10 -- 20  0                          
62D -- 50 35   70                                                         
                 50  0  0  0  25   50                                     
                                      0 --  0  0                          
63D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    95 100                                                
                          90  95  100                                     
                                     75 100                               
                                           100                            
                                              85                          
68D --  0 20   0  0  0  0 60  100 100                                     
                                     90 -- 75 75                          
71D -- 50 40   50                                                         
                 75 40  35                                                
                          75  50   70                                     
                                      0 -- 75 75                          
72D -- 35 60  100                                                         
                 85 50 100                                                
                          25  65  100                                     
                                     35 -- 100                            
                                              35                          
73D -- 90 70  100                                                         
                 95 25  0 70  100 100                                     
                                      0 -- 50 25                          
__________________________________________________________________________
 (--) = Not tested.                                                       

                                  TABLE VII-D                             
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity                             
Application Rate -- 2.24 kg/ha                                            
Cmd.                                                                      
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
 7D 100                                                                   
       100                                                                
          100 100                                                         
                 80  90                                                   
                        10                                                
                           95 100 100                                     
                                     55 100                               
                                           45 100                         
16D.sup.a                                                                 
    100                                                                   
        85                                                                
          35  100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           85  70                         
24D 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           100                            
                                              --                          
29D 100                                                                   
       100                                                                
          60  100                                                         
                 90 100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           100                            
                                              --                          
33D  90                                                                   
        98                                                                
          85  100                                                         
                 100                                                      
                     80                                                   
                       100                                                
                          100 100 100                                     
                                     90 100                               
                                           90 100                         
53D 100                                                                   
       100                                                                
          60  100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           100                            
                                              --                          
57D  25                                                                   
        40                                                                
          10  100                                                         
                 10  0  10                                                
                          100  95 100                                     
                                     35 100                               
                                           -- 100                         
64D.sup.a                                                                 
    --  0  0   90                                                         
                  0  0  85                                                
                           40 100  80                                     
                                     50 -- 35 100                         
66D.sup.a                                                                 
    --  0  0   65                                                         
                  0  0  70                                                
                           75  80  75                                     
                                      0 -- 25  75                         
67D.sup.a                                                                 
    --  0  0   75                                                         
                 35  0  40                                                
                           70  80  60                                     
                                      0 --  0 100                         
69D.sup.a                                                                 
    --  0  0   80                                                         
                 35  0 100                                                
                           90 100 100                                     
                                     40 -- 35 100                         
70D.sup.a                                                                 
    -- 100                                                                
           0  100                                                         
                 70  90                                                   
                        90                                                
                          100 100 100                                     
                                     30 -- 25 100                         
__________________________________________________________________________
 (--) = Not tested.                                                       
 .sup.(a) = Tested at 0.28 kg/ha.                                         

                                  TABLE VIII-D                            
__________________________________________________________________________
Post-Emergence Multi-weed Herbicide Test                                  
Application Rate - 1.12 kg/ha                                             
Cmd.                                                                      
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
34D 90  85                                                                
          30   95                                                         
                 -- 45 98  75 100 100                                     
                                     40 100                               
                                           50 --                          
35D 100                                                                   
        85                                                                
          70  100                                                         
                 -- 90 100                                                
                          100 100 100                                     
                                     40 100                               
                                           75 --                          
40D 75 100                                                                
           5  100                                                         
                 -- 50 75 100 100 100                                     
                                     40 100                               
                                           30 --                          
41D--                                                                     
    -- -- --  -- -- -- -- --  --  -- -- -- -- --                          
42D 40 100                                                                
          35  100                                                         
                 -- 50 80 100 100 100                                     
                                     80 100                               
                                           70 --                          
43D 60  70                                                                
          20  100                                                         
                 -- 55 60 100 100 100                                     
                                     95 100                               
                                           70 --                          
44D -- -- --  -- -- -- -- --  --  -- -- -- -- --                          
45D -- -- --  -- -- -- -- --  --  -- -- -- -- --                          
46D -- -- --  -- -- -- -- --  --  -- -- -- -- --                          
47D 90 100                                                                
          35  100                                                         
                 -- 75 90 100 100 100                                     
                                     25 100                               
                                           45 --                          
48D 80 100                                                                
          60  100                                                         
                 -- 60 80 100 100 100                                     
                                     85 100                               
                                           60 --                          
49D -- -- --  -- -- -- -- --  --  -- -- -- -- --                          
50D 90  80                                                                
          60   95                                                         
                 80 90 100                                                
                          100 100 100                                     
                                     65 100                               
                                           80 --                          
54D 35  50                                                                
          30  100                                                         
                 30 15 90 100 100 100                                     
                                     100                                  
                                        100                               
                                           95 --                          
55D 100                                                                   
       100                                                                
          20  100                                                         
                 90 20 100                                                
                           90 100 100                                     
                                     100                                  
                                        100                               
                                           -- --                          
56D 75  90                                                                
          75   95                                                         
                 90 25 100                                                
                          100 100 100                                     
                                     90 100                               
                                           90 100                         
58D 70 100                                                                
          40  100                                                         
                 95 30 95 100  95 100                                     
                                     95 100                               
                                           95  85                         
59D 90 100                                                                
          95  100                                                         
                 100                                                      
                    50 100                                                
                          100 100 100                                     
                                     95 100                               
                                           100                            
                                               95                         
60D 95 100                                                                
          100 100                                                         
                 100                                                      
                    75 95 100 100 100                                     
                                     95 100                               
                                           100                            
                                              100                         
__________________________________________________________________________
 (--) = Not tested.                                                       

                                  TABLE IX-D                              
__________________________________________________________________________
Post-Emergence Multi-weed Herbicide Test                                  
Application Rate - 0.56 kg/ha                                             
Cmd.                                                                      
No. DB FT ARG WG SHC                                                      
                    WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
61D -- 40  0  50 35  0 40 75  95  100                                     
                                      0 -- 25  50                         
62D -- 35  0  20  0  0 20 35  60  100                                     
                                      0 --  0 100                         
63D 100                                                                   
       100                                                                
          85  98 85 100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        85 85  95                         
68D -- 30 40  85  0 25 60 80  95  100                                     
                                     95 --  0  80                         
71D -- 50  0  80 65  0 75 100 80  100                                     
                                     50 -- 25 100                         
72D -- 90 70  80 50 50 75 85  100 100                                     
                                     90 -- 100                            
                                              100                         
73D -- 100                                                                
          15  100                                                         
                 75 75 85 100 100  90                                     
                                     60 -- 80 100                         
__________________________________________________________________________
 (--) = Not tested.                                                       

                                  TABLE IV-E                              
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 2.24 kg/ha                                             
Cmd.                                                                      
No. DB FT ARG WG JG WO BSG                                                
                          AMG SESB                                        
                                 VL SP                                    
                                      MD YNS                              
__________________________________________________________________________
17E 95 85 35  100                                                         
                 85                                                       
                   25 90 100 100 100                                      
                                    40                                    
                                      100                                 
                                         95                               
18E  0  0  0   50                                                         
                 20                                                       
                    0 15  60  45 100                                      
                                     0                                    
                                      100                                 
                                         --                               
__________________________________________________________________________

                                  TABLE V-E                               
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 1.12 kg/ha                                             
Cmd.                                                                      
No. DB FT ARG WG JG WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
__________________________________________________________________________
 7E 30 70 20  100                                                         
                 75  0 90 100 95  100                                     
                                     100                                  
                                        100                               
                                           90                             
 8E 95 95 45  100                                                         
                 98 25 90 100 95  100                                     
                                     90 100                               
                                           90                             
 9E 10 70 40  100                                                         
                 20  0 80 100 85  100                                     
                                     40 100                               
                                           95                             
10E 100                                                                   
       100                                                                
          10  100                                                         
                 40  0 90 100 100 100                                     
                                     80 100                               
                                           100                            
11E 90 100                                                                
          90  100                                                         
                 100                                                      
                    65 100                                                
                          100 90  100                                     
                                     30 100                               
                                           65                             
12E 100                                                                   
       100                                                                
          80  100                                                         
                 100                                                      
                    85 90 100 100 100                                     
                                     85 100                               
                                           90                             
13E  0 100                                                                
          10  100                                                         
                 100                                                      
                    80 70  80 90  100                                     
                                     70 100"                              
                                           80                             
15E  0 10  0   90                                                         
                  0   0                                                   
                       15  35 30  100                                     
                                     10  85                               
                                           75                             
19E 100                                                                   
       90  0  100                                                         
                 20 10 40  95 100 100                                     
                                     100                                  
                                        100                               
                                           65                             
__________________________________________________________________________

                                  TABLE VI-E                              
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 2.24 kg/ha                                             
Cmd.                                                                      
No. DB FT ARG WG JG                                                       
                   WO BSG                                                 
                         AMG SESB                                         
                                 VL SP                                    
                                      MD YNS                              
__________________________________________________________________________
17E 80 100                                                                
          55  95 90                                                       
                   20 60 100 100 100                                      
                                    75                                    
                                      100                                 
                                         70                               
18E  0 100                                                                
           0  98 20                                                       
                    0 10  70  60 100                                      
                                    10                                    
                                      100                                 
                                         45                               
__________________________________________________________________________

                                  TABLE VII-E                             
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity                             
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG JG WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
__________________________________________________________________________
 7E 25 30  0  70 60 20 90 75   95  85                                     
                                     50 100                               
                                           35                             
 8E 80 80 20  70 70 40 80 50   80  80                                     
                                     60 60 35                             
 9E  0 30  0  75 15 25 100                                                
                          95  100 100                                     
                                     60 100                               
                                           25                             
10E 60 80 20  70 35 25 80 75   90  90                                     
                                     70 100                               
                                           45                             
11E 45 100                                                                
          20  100                                                         
                 100                                                      
                    40 50 100 100 100                                     
                                     20 100                               
                                           35                             
12E 70 60 30  100                                                         
                 100                                                      
                    80 98 90  100 100                                     
                                     70 98 40                             
13E 25 100                                                                
          10  100                                                         
                 100                                                      
                    85 100                                                
                          80  100 100                                     
                                     10 90 25                             
15E 30 65 10  90 50 30 20 85   80  98                                     
                                     30 65 15                             
19E 20 60 10  90 10 15 90 100 100  70                                     
                                     100                                  
                                        40 85                             
__________________________________________________________________________

                                  TABLE IV-F                              
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 1.12 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG JG WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
19F 40 35 60  100                                                         
                 90 30 90 100 100 -- 20 100                               
                                           90 --                          
26F 25 70 45  95 60 25 85 35  75  -- 20 100                               
                                           95 90                          
27F 45 65 40  100                                                         
                 60 25 80 100 85  100                                     
                                     40 100                               
                                           95 35                          
28F 80 100                                                                
          90  100                                                         
                 100                                                      
                    90 100                                                
                          70  90  100                                     
                                     30 100                               
                                           95 35                          
29F 90 45 75  100                                                         
                 85 40 90 95  90  100                                     
                                     40 100                               
                                           95 --                          
30F 90 45 75  100                                                         
                 90 75 100                                                
                          100 80  100                                     
                                     60 100                               
                                           95 --                          
31F 60 65 75  100                                                         
                 100                                                      
                    55 95 100 100 100                                     
                                     100                                  
                                        100                               
                                           95 --                          
32F 90 100                                                                
          90  100                                                         
                 100                                                      
                    65 85 100 90  100                                     
                                     95 100                               
                                           85 --                          
33F 100                                                                   
       100                                                                
          95  100                                                         
                 100                                                      
                    95 100                                                
                          100 100 100                                     
                                     25 100                               
                                           90 --                          
35F 90 100                                                                
          100 100                                                         
                 -- 90 90 100 90  100                                     
                                     10 100                               
                                           75 --                          
36F 90 35 85  100                                                         
                 -- 15 80 95  90  100                                     
                                     50 100                               
                                           95 --                          
39F 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    95 100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           98 --                          
40F 100                                                                   
       100                                                                
          80  100                                                         
                 100                                                      
                    70 100                                                
                          100 100 100                                     
                                     90 100                               
                                           95 --                          
41F 100                                                                   
       100                                                                
          100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     60 100                               
                                           98 --                          
42F 60 100                                                                
          85  100                                                         
                 100                                                      
                    70 95 100 95  100                                     
                                     10 100                               
                                           95 50                          
43F 85 100                                                                
          25  100                                                         
                 60 25 98 100 100 100                                     
                                     100                                  
                                        100                               
                                           90 100                         
44F 0  80 10  85 0  0  75 0   30  100                                     
                                     0  100                               
                                           0  10                          
45F 25 100                                                                
          40  100                                                         
                 60 0  65 60  60  100                                     
                                     50 100                               
                                           70 0                           
50F -- 100                                                                
          50  100                                                         
                 35 35 75     100 100                                     
                                     --                                   
__________________________________________________________________________
 (--) = Not tested.                                                       

                                  TABLE V-F                               
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test                                   
Application Rate - 0.56 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG JG WO BSG                                                
                          AMG SESB                                        
                                  VL SP                                   
                                       MD YNS                             
                                             CB                           
__________________________________________________________________________
46F 0  65 35  75 65 0   0  0  35  100                                     
                                     25                                   
                                       90 80  0                           
47F -- 60 35  100                                                         
                 100                                                      
                    0  90 100 100 100                                     
                                     70                                   
                                       -- 100                             
                                             75                           
48F -- 75 20  90 60 0  15 70  35  90 0 -- 20 40                           
49F -- 60 10  100                                                         
                 60 0  50 100 95  100                                     
                                     40                                   
                                       -- 90 100                          
51F -- 40 10  95 40 10 50 65  100 100                                     
                                     0 -- 95 65                           
__________________________________________________________________________
 (--)  Not tested.                                                        

                                  TABLE VI-F                              
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity                             
Application Rate - 2.24 kg/ha                                             
Cmpd.                                                                     
No. DB FT ARG WG JG WO BSG                                                
                          AMG SESB                                        
                                  VL SP MD YNS                            
                                              CB                          
__________________________________________________________________________
19F 100                                                                   
       90 65  100                                                         
                 100                                                      
                    98 100                                                
                          100 100 100                                     
                                     60 100                               
                                           70 100                         
26F 60 75 60  95 45 50 90 50  90  100                                     
                                     40 90 60 --                          
27F 80 70 65  95 100                                                      
                    90 100                                                
                          100 100 100                                     
                                     85 100                               
                                           75 --                          
28F 80 100                                                                
          75  90 85 80 100                                                
                          80  80  100                                     
                                     30 100                               
                                           85 85                          
29F 85 70 55  90 98 90 100                                                
                          100 100 100                                     
                                     35 100                               
                                           60 100                         
30F 90 80 40  90 85 80 80 70  100 100                                     
                                     20 100                               
                                           40 --                          
31F 100                                                                   
       80 20  100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           85 --                          
32F 70 90 60  100                                                         
                 100                                                      
                    98 100                                                
                          100 100 100                                     
                                     100                                  
                                        100                               
                                           60 --                          
33F 95 100                                                                
          80  100                                                         
                 90 100                                                   
                       100                                                
                          100 100 100                                     
                                     70 100                               
                                           40 --                          
35F 70 90 40  100                                                         
                 -- 100                                                   
                       100                                                
                          100 100 100                                     
                                     98 100                               
                                           30 --                          
36F 85 100                                                                
       35 100 -- 20 100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        15 --                             
39F 100 100                                                               
       85 100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 100                                     
                                     100                                  
                                        90 100                            
40F 100 100                                                               
       30 100 100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100 100 90 100                                  
                                        75 --                             
41F 100 100                                                               
       35 90  70 100                                                      
                    90 100                                                
                          100 100 50 100                                  
                                        70 --                             
42F 45 100                                                                
          50  100                                                         
                 70 55 80 100 100 100                                     
                                     70 100                               
                                           75 100                         
43F 25 80 15  98 35 0  20 100 100 100                                     
                                     100                                  
                                        100                               
                                           60 95                          
44F 0  15 0   65 0  0  0  70  100 100                                     
                                     40 100                               
                                           0  100                         
45F 0  75 35  70 35 0  60 50  85  100                                     
                                     50 100                               
                                           75 70                          
50F -- 40 0   75 45 40 60 100 100 95 30 -- 60 100                         
__________________________________________________________________________
 (--) = Not tested.                                                       

                                  TABLE VII-F                             
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity                             
Application Rate - 0.56 kg/ha                                             
Cmd.                                                                      
No. DB FT ARG WG JG                                                       
                   WO BSG                                                 
                         AMG SESB                                         
                                 VL SP                                    
                                      MD YNS                              
                                            CB                            
__________________________________________________________________________
46F 25 35 20  50 35                                                       
                   35  0 20   75 100                                      
                                    35                                    
                                      95 -- 50                            
47F -- 75 25  90 40                                                       
                   25 80 100 100 100                                      
                                    80                                    
                                      -- 75 100                           
48F -- 50 35  80 35                                                       
                   40 0  75  100 85 15                                    
                                      -- 50 75                            
49F -- 35 0   75 30                                                       
                   0  20 100 100 100                                      
                                    80                                    
                                      -- 25 85                            
51F -- 35 0   80 35                                                       
                   20 70 50  95  95 25                                    
                                      -- 65 50                            
__________________________________________________________________________
 (--) = Not Tested.
The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as graules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.
Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.
Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.
Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 0.1% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
Typical wetting, dispersing or emulsifing agents and adjuvants used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 30% by weight of the herbicidal composition.
Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.
Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredients by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.
Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.
The phytotoxic compositions of this invention can be applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.
______________________________________                                    
EMULSIFIABLE CONCENTRATE FORMULATIONS                                     
General Formula with Ranges                                               
                 Specific Formula                                         
______________________________________                                    
Herbicidal compound                                                       
              5-55   herbicidal compound                                  
                                     24                                   
surfactant(s)                                                             
              5-25   proprietary blend of oil-                            
                                     10                                   
solvent(s)   20-90   soluble sulfonates and                               
             100%    polyoxyethylene ethers                               
                     polar solvent   27                                   
                     petroleum hydrocarbon                                
                                     39                                   
                                     100%                                 
______________________________________                                    

______________________________________                                    
WETTABLE POWDER FORMULATIONS                                              
______________________________________                                    
herbicidal compound                                                       
              3-90   herbicidal compound                                  
                                     80                                   
wetting agent                                                             
             0.5-2   sodium dialkyl naphtha-                              
                                     0.5                                  
dispersing agent                                                          
             1-8     lene sulfonate                                       
diluent(s)   8.5-87  sodium lignosulfonate                                
                                     7                                    
             100%    attapulgite clay                                     
                                     12.5                                 
                                     100%                                 
______________________________________                                    

______________________________________                                    
EXTRUDED GRANULAR FORMULATIONS                                            
______________________________________                                    
herbicidal compound                                                       
              1-20   herbicidal compound                                  
                                     10                                   
binding agent                                                             
              0-10   lignin sulfonate                                     
                                      5                                   
diluent(s)   70-99   calcium carbonate                                    
                                     85                                   
             100%                    100%                                 
______________________________________                                    

______________________________________                                    
FLOWABLE FORMULATIONS                                                     
______________________________________                                    
herbicidal compound                                                       
             20-70     herbicidal compound                                
                                     45                                   
surfactant(s)                                                             
              1-10     polyoxyethylene                                    
                                     5                                    
                       ether                                              
suspending agent(s)                                                       
             0.05-1    attagel       0.05                                 
antifreeze agent                                                          
              1-10     propylene glycol                                   
                                     10                                   
antimicrobial agent                                                       
              1-10     1,2-benzisothiazo-                                 
                                     0.03                                 
                       line-3-one                                         
antifoam agent                                                            
             0.1-1     silicone defoamer                                  
                                     0.02                                 
solvent       7.95-77.85                                                  
                       water         39.9                                 
             100%                    100%                                 
______________________________________
When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.
The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate.

Claims (7)

We claim:
1. Compound having the structural formula ##STR96## wherein R and R1 are hydrogen, C1 -C4 alkyl, Ra OC(O)--, where Ra is C1 -C4 alkyl;
R2 is C1 -C4 alkoxy; and
R3, R4 and R5 independently are (1) hydrogen; (2) halogen; (3) C1 -C4 alkyl; (4) C1 -C4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C1 -C4 haloalkyl; (9) Rb SOn -- wherein Rb is C1 -C4 alkyl, C1 -C4 haloalkyl, phenyl, benzyl, --NRd Re wherein Rd and Re independently are hydrogen or C1 -C4 alkyl; and n is the integer 0, 1 or 2; ##STR97## wherein Rc is C1 -C4 alkyl and Rj is hydrogen; (11) Rf C(O) wherein Rf is hydrogen, C1 -C4 alkyl, C1 -C4 haloalkyl, C1 -C4 alkoxy; (12) --NRg Rh wherein Rg and Rh independently are hydrogen or C1 -C4 alkyl; or (13) R3 and R4 together can form a ring structure with two adjacent carbon atoms of the phenyl ring; and their salts.
2. The compound of claim 1 wherein R and R1 are hydrogen or C1 -C4 alkyl; R2 is C1 -C4 alkoxy; R3 and R4 independently are hydrogen, halogen, C1 -C4 alkyl, C1 -C4 alkoxy, trifluoromethoxy, cyano, nitro, C1 -C4 haloalkyl, Rb SOn wherein Rb is C1 -C4 alkyl, C1 -C4 haloalkyl, phenyl, benzyl, --NRd Re wherein Rd and Re independently are hydrogen and C1 -C4 alkyl; and n is the integer 0, 1 or 2; Rc C(O)NH-- wherein Rc is C1 -C4 alkyl; Rf C(O)-- wherein Rf is hydrogen, C1 -C4 alkyl, C1 -C4 haloalkyl, C1 -C4 alkoxy; or --NRg Rh wherein Rg and Rh independently are hydrogen or C1 -C4 alkyl; and R5 is hydrogen and their salts.
3. The compound of claim 1 wherein R and R1 are hydrogen or C1 -C4 alkyl; R2 is C1 -C4 alkoxy; R3 is hydrogen, halogen, C1 -C4 alkyl, C1 -C4 alkoxy, nitro, C1 -C4 haloalkyl or Rb SOn wherein Rb is C1 -C4 alkyl and n is the integer 0; R4 is hydrogen, halogen, C1 -C4 alkyl, C1 -C4 alkoxy, cyano, nitro, C1 -C4 haloalkyl or Rb SOn wherein Rb is C1 -C4 alkyl and n is the integer 0, 1 or 2; and R5 is hydrogen and their salts.
4. The compound of claim 1 wherein R and R1 are hydrogen or methyl; R2 is methoxy; R3 is hydrogen, halogen, methyl, C1 -C4 alkoxy, nitro, trifluoromethyl or methylthio; R4 is hydrogen, halogen, methyl, methoxy, cyano, nitro, trifluoromethyl, methylthio or CH3 SO2 ; and R5 is hydrogen and their salts.
5. The compound of claim 3 wherein R3 is in the 3-position and R4 is in the 4-position and their salts.
6. The compound of claim 4 wherein R3 is in the 3-position and R4 is in the 4-position and their salts.
7. The compound of claim 1 wherein R and R1 are hydrogen or C1 -C4 alkyl; R2 is C1 -C4 alkoxy; R3 is hydrogen, halogen, C1 -C4 alkoxy, or Rb SOn wherein Rb is C1 -C4 alkyl and n is the integer 0; R4 is Rb SOn -- wherein Rb is C1 -C4 alkyl and n is the integer 2; and R5 is hydrogen.
US07/211,782 1982-03-25 1988-06-27 Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones Expired - Lifetime US4946981A (en)

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Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US36165882A 1982-03-25 1982-03-25
US46425183A 1983-02-09 1983-02-09
US53288283A 1983-09-16 1983-09-16
US53286983A 1983-09-16 1983-09-16
US56607783A 1983-12-27 1983-12-27
US58733184A 1984-03-07 1984-03-07
US63440884A 1984-07-31 1984-07-31
US64079184A 1984-08-17 1984-08-17
US68388484A 1984-12-20 1984-12-20
US68390084A 1984-12-20 1984-12-20
US06/880,370 US4780127A (en) 1982-03-25 1986-06-30 Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides
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EP0517660A1 (en) * 1991-06-05 1992-12-09 Ciba-Geigy Ag Benzo-1,2,3-thiadiazole derivatives
US5306695A (en) * 1991-03-06 1994-04-26 Hoechst Aktiengesellschaft Haloalkoxy-substituted benzoylcyclohexanediones as herbicides and plant growth regulators
US5728889A (en) * 1995-01-25 1998-03-17 Zeneca Limited Process for the production of 2-(substituted benzoyl)-1,3 cyclohexanediones
WO2000034288A1 (en) * 1998-12-08 2000-06-15 E.I. Du Pont De Nemours And Company Process for removal of cyanide from reactions producing 1,3 diones
US6372693B1 (en) 1997-05-07 2002-04-16 Basf Aktiengesellschaft Substituted 2-(3-alkenyl-benzoyl)-cyclohexane-1,3-diones
US6610631B1 (en) 1999-09-30 2003-08-26 Bayer Aktiengesellschaft Substituted aryl ketones
US20040082481A1 (en) * 2001-02-15 2004-04-29 Griffiths Andrew John Agrochemical formulation
US20040097376A1 (en) * 2000-07-29 2004-05-20 Klaus-Helmut Muller Substituted aryl ketones and their use as herbicides
US20040176253A1 (en) * 2001-05-09 2004-09-09 Stefan Hermann Substitued arylketones
US20050009704A1 (en) * 2000-01-17 2005-01-13 Otto Schallner Substituted aryl ketones
US20050119129A1 (en) * 2002-02-19 2005-06-02 Hans-Georg Schwarz Substituted aryl ketones
US20050143261A1 (en) * 2002-03-22 2005-06-30 Dieter Feucht Selective herbicides based on substituted aminotrizinones and substituted benzoyl-cyclohexandionen
US20050153958A1 (en) * 2002-03-05 2005-07-14 Dorothee Hoischen Substituted aryl ketones
US20090042730A1 (en) * 2001-05-09 2009-02-12 Stefan Herrmann Substituted Arylketones
US7670991B2 (en) 2001-05-16 2010-03-02 Bayer Cropscience Ag Substituted benzoylcyclohexenones and their use as herbicidal agents
WO2010104090A1 (en) * 2009-03-11 2010-09-16 住友化学株式会社 Herbicide composition and weed control method

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Cited By (28)

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Publication number Priority date Publication date Assignee Title
US5306695A (en) * 1991-03-06 1994-04-26 Hoechst Aktiengesellschaft Haloalkoxy-substituted benzoylcyclohexanediones as herbicides and plant growth regulators
EP0517660A1 (en) * 1991-06-05 1992-12-09 Ciba-Geigy Ag Benzo-1,2,3-thiadiazole derivatives
US5248683A (en) * 1991-06-05 1993-09-28 Ciba-Geigy Corporation Benzo-1,2,3-thiadiazole derivatives
US5728889A (en) * 1995-01-25 1998-03-17 Zeneca Limited Process for the production of 2-(substituted benzoyl)-1,3 cyclohexanediones
US6372693B1 (en) 1997-05-07 2002-04-16 Basf Aktiengesellschaft Substituted 2-(3-alkenyl-benzoyl)-cyclohexane-1,3-diones
WO2000034288A1 (en) * 1998-12-08 2000-06-15 E.I. Du Pont De Nemours And Company Process for removal of cyanide from reactions producing 1,3 diones
US6610631B1 (en) 1999-09-30 2003-08-26 Bayer Aktiengesellschaft Substituted aryl ketones
US6727206B2 (en) 1999-09-30 2004-04-27 Bayer Aktiengesellschaft Substituted aryl ketones
US20040162326A1 (en) * 1999-09-30 2004-08-19 Klaus-Helmut Muller Substituted aryl ketones
US20050009704A1 (en) * 2000-01-17 2005-01-13 Otto Schallner Substituted aryl ketones
US6864219B2 (en) 2000-01-17 2005-03-08 Bayer Aktiengesellschaft Substituted aryl ketones
US20040097376A1 (en) * 2000-07-29 2004-05-20 Klaus-Helmut Muller Substituted aryl ketones and their use as herbicides
US20040082481A1 (en) * 2001-02-15 2004-04-29 Griffiths Andrew John Agrochemical formulation
US7666816B2 (en) * 2001-02-15 2010-02-23 Syngenta Limited Agrochemical formulation
US20090042730A1 (en) * 2001-05-09 2009-02-12 Stefan Herrmann Substituted Arylketones
US7456133B2 (en) 2001-05-09 2008-11-25 Bayer Cropscience Ag Substituted arylketones
US20040176253A1 (en) * 2001-05-09 2004-09-09 Stefan Hermann Substitued arylketones
US7112554B2 (en) 2001-05-09 2006-09-26 Bayer Cropscience Ag Substituted arylketones
US20060252647A1 (en) * 2001-05-09 2006-11-09 Stefan Herrmann Substituted arylketones
US7670991B2 (en) 2001-05-16 2010-03-02 Bayer Cropscience Ag Substituted benzoylcyclohexenones and their use as herbicidal agents
US7153813B2 (en) 2002-02-19 2006-12-26 Bayer Aktiengesellschaft Substituted aryl ketones
US20050119129A1 (en) * 2002-02-19 2005-06-02 Hans-Georg Schwarz Substituted aryl ketones
US20050153958A1 (en) * 2002-03-05 2005-07-14 Dorothee Hoischen Substituted aryl ketones
US7807703B2 (en) 2002-03-05 2010-10-05 Bayer Cropscience Ag Substituted aryl ketones
US7612017B2 (en) 2002-03-22 2009-11-03 Bayer Cropscience Ag Selective herbicides based on substituted aminotriazinones and substituted benzoylcyclohexanediones
US20050143261A1 (en) * 2002-03-22 2005-06-30 Dieter Feucht Selective herbicides based on substituted aminotrizinones and substituted benzoyl-cyclohexandionen
WO2010104090A1 (en) * 2009-03-11 2010-09-16 住友化学株式会社 Herbicide composition and weed control method
CN102348379A (en) * 2009-03-11 2012-02-08 住友化学株式会社 Herbicidal composition and method for controlling weeds

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